Catalysts for (e)-selective olefin metathesis

ABSTRACT

This invention relates generally to olefin metathesis catalyst compounds, to the preparation of such compounds, and the use of such catalysts in the metathesis of olefins and olefin compounds, more particularly, in the use of such catalysts in (E)-selective olefin metathesis reactions. The invention has utility in the fields of catalysis, organic synthesis, polymer chemistry, and industrial and fine chemicals chemistry.

RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional PatentApplication No. 62/135,797, filed Mar. 20, 2015, and of U.S. ProvisionalPatent Application No. 62/180,183, filed Jun. 16, 2015, the contents ofeach are incorporated herein by reference.

STATEMENT OF FEDERAL SUPPORT

This invention was made with government support under GM031332 awardedby the National Institutes of Health and CHE1212767 awarded by theNational Science Foundation. The government has certain rights in theinvention.

TECHNICAL FIELD

This invention relates generally to olefin metathesis catalystcompounds, to the preparation of such compounds, and the use of suchcatalysts in the metathesis of olefins and olefin compounds, moreparticularly, in the use of such catalysts in (E)-selective olefinmetathesis reactions. The invention has utility in the fields ofcatalysis, organic synthesis, polymer chemistry, and industrial and finechemicals chemistry.

BACKGROUND

Since its discovery in the 1950s, olefin metathesis has emerged as avaluable synthetic method for the formation of carbon-carbon doublebonds. In particular, its recent advances in applications to organicsyntheses and polymer syntheses mostly rely on developments ofwell-defined catalysts. Among attempts to improve catalyst efficiencyover the past decade, one of the most attractive frontiers has beenselective synthesis of stereo-controlled olefin products. Most catalystsgive higher proportion of thermodynamically favored (E) isomer of olefinproducts.

SUMMARY OF THE DISCLOSURE

The invention is directed to addressing one or more of theaforementioned concerns, and, in one embodiment, provides metal carbeneolefin metathesis catalysts that may be used in the invention disclosedherein. The metal carbene olefin metathesis catalysts are preferablyGroup 8 transition metal complexes. The invention is also directed to amethod of preparing the metal carbene olefin metathesis catalysts, ofthe invention.

In one embodiment the present invention provides metal carbene olefinmetathesis catalysts for (E)-selective olefin metathesis.

In another embodiment the present invention provides metal carbeneolefin metathesis catalysts for (E)-selective ring opening metathesispolymerization (ROMP).

In another embodiment the present invention provides metal carbeneolefin metathesis catalysts for (E)-selective ring opening crossmetathesis (ROCM).

In another embodiment the present invention provides metal carbeneolefin metathesis catalysts for (E)-selective cross metathesis (CM).

In another embodiment the present invention provides metal carbeneolefin metathesis catalysts for (E)-selective ring closing metathesis(RCM).

In another embodiment the present invention provides a method forperforming a metathesis reaction comprising, contacting at least oneolefin with a metal carbene olefin metathesis catalyst of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the ¹H-NMR array experiment in the ROCM reaction of2,3-dihydrofuran with catalyst (3)-rac, as shown in Table 1 entry 3.

FIG. 2 summarizes the progress of the reaction of Example 3a; ROCMreaction of norbornene (12) to product (13) as shown in Scheme 8, usingcatalyst C848 (2) and catalyst (3)-rac.

FIG. 3 summarizes the (E/Z) selectivity of product (13) versusconversion, of Example 3a as shown in Scheme 8, using catalyst C848 (2)and catalyst (3)-rac.

FIG. 4 summarizes the (E/Z) selectivity of product (13) versus time, ofExample 3a as shown in Scheme 8, using catalyst C848 (2) and catalyst(3)-rac.

FIG. 5 summarizes the conversion to product (9) of the RCM reaction ofExample 2a shown in Scheme 6, using catalyst C848 (2) and catalyst(3)-rac.

FIG. 6 summarizes the Log plots for catalyst C848 (2) and catalyst(3)-rac in the RCM reaction of Example 2a as shown in Scheme 6.

FIG. 7 summarizes the conversion in ROMP reaction of cyclooctene inExample 3b as shown in Scheme 9, using catalyst C848 (2) and catalyst(3)-rac.

FIG. 8 summarizes the Log plots for catalyst C848 (2) and catalyst(3)-rac in the ROMP of cyclooctene of Example 3b as shown in Scheme 9.

FIG. 9 shows the X-ray crystal structure of catalyst (16)-rac. Thecrystal structure is shown with 50% probability ellipsoids. Hydrogensare omitted for clarity. Two different orientations of the molecule areshown due to disorder over several atoms.

FIG. 10 shows the X-ray crystal structure of catalyst (16)-meso.

FIG. 11 shows the ¹H NMR peaks of the allylic protons of substrate (18)and of product (19) as shown in Example 4a, reaction of Scheme 10.

FIG. 12 shows the ¹H NMR peaks of the allylic protons of substrate (20)and of product (21) as shown in Example 4a, reaction of Scheme 11.

FIG. 13 shows the (E/Z) ratio of product (19) versus the conversion (%)in the cross metathesis of 5-decene with (18), as shown in Example 4a,reaction of Scheme 10.

FIG. 14 shows the (E/Z) ratio of product (21) versus the conversion (%)in the cross metathesis of 5-decene with (20), as shown in Example 4a,reaction of Scheme 11.

DETAILED DESCRIPTION OF THE DISCLOSURE Terminology and Definitions

Unless otherwise indicated, the invention is not limited to specificreactants, substituents, catalysts, reaction conditions, or the like, assuch may vary. It is also to be understood that the terminology usedherein is for the purpose of describing particular embodiments only andis not to be interpreted as being limiting.

As used in the specification and the appended claims, the singular forms“a,” “an,” and “the” include plural referents unless the context clearlydictates otherwise. Thus, for example, reference to “an α-olefin”includes a single α-olefin as well as a combination or mixture of two ormore α-olefins, reference to “a substituent” encompasses a singlesubstituent as well as two or more substituents, and the like.

As used in the specification and the appended claims, the terms “forexample,” “for instance,” “such as,” or “including” are meant tointroduce examples that further clarify more general subject matter.Unless otherwise specified, these examples are provided only as an aidfor understanding the invention, and are not meant to be limiting in anyfashion.

In this specification and in the claims that follow, reference will bemade to a number of terms, which shall be defined to have the followingmeanings:

The term “alkyl” as used herein refers to a linear, branched, or cyclicsaturated hydrocarbon group typically although not necessarilycontaining 1 to about 24 carbon atoms, preferably 1 to about 12 carbonatoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,t-butyl, octyl, decyl, and the like, as well as cycloalkyl groups suchas cyclopentyl, cyclohexyl and the like. Generally, although again notnecessarily, alkyl groups herein contain 1 to about 12 carbon atoms. Theterm “lower alkyl” intends an alkyl group of 1 to 6 carbon atoms, andthe specific term “cycloalkyl” intends a cyclic alkyl group, typicallyhaving 4 to 8, preferably 5 to 7, carbon atoms. The term “substitutedalkyl” refers to alkyl substituted with one or more substituent groups,and the terms “heteroatom-containing alkyl” and “heteroalkyl” refer toalkyl in which at least one carbon atom is replaced with a heteroatom.If not otherwise indicated, the terms “alkyl” and “lower alkyl” includelinear, branched, cyclic, unsubstituted, substituted, and/orheteroatom-containing alkyl and lower alkyl, respectively.

The term “alkylene” as used herein refers to a difunctional linear,branched, or cyclic alkyl group, where “alkyl” is as defined above.

The term “alkenyl” as used herein refers to a linear, branched, orcyclic hydrocarbon group of 2 to about 24 carbon atoms containing atleast one double bond, such as ethenyl, n-propenyl, isopropenyl,n-butenyl, isobutenyl, octenyl, decenyl, tetradecenyl, hexadecenyl,eicosenyl, tetracosenyl, and the like. Preferred alkenyl groups hereincontain 2 to about 12 carbon atoms. The term “lower alkenyl” intends analkenyl group of 2 to 6 carbon atoms, and the specific term“cycloalkenyl” intends a cyclic alkenyl group, preferably having 5 to 8carbon atoms. The term “substituted alkenyl” refers to alkenylsubstituted with one or more substituent groups, and the terms“heteroatom-containing alkenyl” and “heteroalkenyl” refer to alkenyl inwhich at least one carbon atom is replaced with a heteroatom. If nototherwise indicated, the terms “alkenyl” and “lower alkenyl” includelinear, branched, cyclic, unsubstituted, substituted, and/orheteroatom-containing alkenyl and lower alkenyl, respectively. The term“alkenyl” is used interchangeably with the term “olefin” herein.

The geometry of the olefins described in this patent application may beof (E) conformation, or of (Z) conformation, or of a mixture of (E) and(Z) conformations. Applicants have represented a mixture of double-bondisomers by using a squiggly bond

For example, as represented herein, structure

exemplifies either the (E) conformation

or the (Z) conformation

or can represent a mixture of (E) and (Z) conformations.

The term “(E/Z) ratio” refers to proportion of (E) isomer versus (Z)isomer.

The term “alkenylene” as used herein refers to a difunctional linear,branched, or cyclic alkenyl group, where “alkenyl” is as defined above.

The term “alkynyl” as used herein refers to a linear or branchedhydrocarbon group of 2 to about 24 carbon atoms containing at least onetriple bond, such as ethynyl, n-propynyl, and the like. Preferredalkynyl groups herein contain 2 to about 12 carbon atoms. The term“lower alkynyl” intends an alkynyl group of 2 to 6 carbon atoms. Theterm “substituted alkynyl” refers to alkynyl substituted with one ormore substituent groups, and the terms “heteroatom-containing alkynyl”and “heteroalkynyl” refer to alkynyl in which at least one carbon atomis replaced with a heteroatom. If not otherwise indicated, the terms“alkynyl” and “lower alkynyl” include linear, branched, unsubstituted,substituted, and/or heteroatom-containing alkynyl and lower alkynyl,respectively.

The term “alkoxy” as used herein intends an alkyl group bound through asingle, terminal ether linkage; that is, an “alkoxy” group may berepresented as —O-alkyl where alkyl is as defined above. A “loweralkoxy” group intends an alkoxy group containing 1 to 6 carbon atoms.Analogously, “alkenyloxy” and “lower alkenyloxy” respectively refer toan alkenyl and lower alkenyl group bound through a single, terminalether linkage, and “alkynyloxy” and “lower alkynyloxy” respectivelyrefer to an alkynyl and lower alkynyl group bound through a single,terminal ether linkage.

The term “aryl” as used herein, and unless otherwise specified, refersto an aromatic substituent containing a single aromatic ring or multiplearomatic rings that are fused together, directly linked, or indirectlylinked (such that the different aromatic rings are bound to a commongroup such as a methylene or ethylene moiety). Preferred aryl groupscontain 5 to 24 carbon atoms, and particularly preferred aryl groupscontain 5 to 14 carbon atoms. Exemplary aryl groups contain one aromaticring or two fused or linked aromatic rings, e.g., phenyl, naphthyl,biphenyl, diphenylether, diphenylamine, benzophenone, and the like.“Substituted aryl” refers to an aryl moiety substituted with one or moresubstituent groups, and the terms “heteroatom-containing aryl” and“heteroaryl” refer to aryl substituents in which at least one carbonatom is replaced with a heteroatom, as will be described in furtherdetail infra.

The term “aryloxy” as used herein refers to an aryl group bound througha single, terminal ether linkage, wherein “aryl” is as defined above. An“aryloxy” group may be represented as —O-aryl where aryl is as definedabove. Preferred aryloxy groups contain 5 to 24 carbon atoms, andparticularly preferred aryloxy groups contain 5 to 14 carbon atoms.Examples of aryloxy groups include, without limitation, phenoxy,o-halo-phenoxy, m-halo-phenoxy, p-halo-phenoxy, o-methoxy-phenoxy,m-methoxy-phenoxy, p-methoxy-phenoxy, 2,4-dimethoxy-phenoxy,3,4,5-trimethoxy-phenoxy, and the like.

The term “alkaryl” refers to an aryl group with an alkyl substituent,and the term “aralkyl” refers to an alkyl group with an arylsubstituent, wherein “aryl” and “alkyl” are as defined above. Preferredalkaryl and aralkyl groups contain 6 to 24 carbon atoms, andparticularly preferred alkaryl and aralkyl groups contain 6 to 16 carbonatoms. Alkaryl groups include, for example, p-methylphenyl,2,4-dimethylphenyl, p-cyclohexylphenyl, 2,7-dimethylnaphthyl,7-cyclooctylnaphthyl, 3-ethyl-cyclopenta-1,4-diene, and the like.Examples of aralkyl groups include, without limitation, benzyl,2-phenyl-ethyl, 3-phenyl-propyl, 4-phenyl-butyl, 5-phenyl-pentyl,4-phenylcyclohexyl, 4-benzylcyclohexyl, 4-phenylcyclohexylmethyl,4-benzylcyclohexylmethyl, and the like. The terms “alkaryloxy” and“aralkyloxy” refer to substituents of the formula —OR wherein R isalkaryl or aralkyl, respectively, as just defined.

The term “acyl” refers to substituents having the formula —(CO)-alkyl,—(CO)-aryl, or —(CO)-aralkyl, and the term “acyloxy” refers tosubstituents having the formula —O(CO)-alkyl, —O(CO)-aryl, or—O(CO)-aralkyl, wherein “alkyl,” “aryl,” and “aralkyl” are as definedabove.

The terms “cyclic” and “ring” refer to alicyclic or aromatic groups thatmay or may not be substituted and/or heteroatom containing, and that maybe monocyclic, bicyclic, or polycyclic. The term “alicyclic” is used inthe conventional sense to refer to an aliphatic cyclic moiety, asopposed to an aromatic cyclic moiety, and may be monocyclic, bicyclic,or polycyclic.

The terms “halo,” “halogen,” and “halide” are used in the conventionalsense to refer to a chloro, bromo, fluoro, or iodo substituent.

“Hydrocarbyl” refers to univalent hydrocarbyl radicals containing 1 toabout 30 carbon atoms, preferably 1 to about 24 carbon atoms, mostpreferably 1 to about 12 carbon atoms, including linear, branched,cyclic, saturated, and unsaturated species, such as alkyl groups,alkenyl groups, aryl groups, and the like. The term “lower hydrocarbyl”intends a hydrocarbyl group of 1 to 6 carbon atoms, preferably 1 to 4carbon atoms, and the term “hydrocarbylene” intends a divalenthydrocarbyl moiety containing 1 to about 30 carbon atoms, preferably 1to about 24 carbon atoms, most preferably 1 to about 12 carbon atoms,including linear, branched, cyclic, saturated and unsaturated species.The term “lower hydrocarbylene” intends a hydrocarbylene group of 1 to 6carbon atoms. “Substituted hydrocarbyl” refers to hydrocarbylsubstituted with one or more substituent groups, and the terms“heteroatom-containing hydrocarbyl” and “heterohydrocarbyl” refer tohydrocarbyl in which at least one carbon atom is replaced with aheteroatom. Similarly, “substituted hydrocarbylene” refers tohydrocarbylene substituted with one or more substituent groups, and theterms “heteroatom-containing hydrocarbylene” and “heterohydrocarbylene”refer to hydrocarbylene in which at least one carbon atom is replacedwith a heteroatom. Unless otherwise indicated, the term “hydrocarbyl”and “hydrocarbylene” are to be interpreted as including substitutedand/or heteroatom-containing hydrocarbyl and hydrocarbylene moieties,respectively.

The term “heteroatom-containing” as in a “heteroatom-containinghydrocarbyl group” refers to a hydrocarbon molecule or a hydrocarbylmolecular fragment in which one or more carbon atoms is replaced with anatom other than carbon, e.g., nitrogen, oxygen, sulfur, phosphorus orsilicon, typically nitrogen, oxygen or sulfur. Similarly, the term“heteroalkyl” refers to an alkyl sub stituent that isheteroatom-containing, the term “heterocyclic” refers to a cyclicsubstituent that is heteroatom-containing, the terms “heteroaryl” and“heteroaromatic” respectively refer to “aryl” and “aromatic”substituents that are heteroatom-containing, and the like. It should benoted that a “heterocyclic” group or compound may or may not bearomatic, and further that “heterocycles” may be monocyclic, bicyclic,or polycyclic as described above with respect to the term “aryl.”Examples of heteroalkyl groups include alkoxyaryl,alkylsulfanyl-substituted alkyl, N-alkylated amino alkyl, and the like.Examples of heteroaryl substituents include pyrrolyl, pyrrolidinyl,pyridinyl, quinolinyl, indolyl, pyrimidinyl, imidazolyl,1,2,4-triazolyl, tetrazolyl, etc., and examples of heteroatom-containingalicyclic groups are pyrrolidino, morpholino, piperazino, piperidino,etc.

By “substituted” as in “substituted hydrocarbyl,” “substituted alkyl,”“substituted aryl,” and the like, as alluded to in some of theaforementioned definitions, is meant that in the hydrocarbyl, alkyl,aryl, or other moiety, at least one hydrogen atom bound to a carbon (orother) atom is replaced with one or more non-hydrogen substituents.Examples of such substituents include, without limitation: functionalgroups referred to herein as “Fn,” such as halo, hydroxyl, sulfhydryl,C₁-C₂₄ alkoxy, C₂-C₂₄ alkenyloxy, C₂-C₂₄ alkynyloxy, C₅-C₂₄ aryloxy,C₆-C₂₄ aralkyloxy, C₆-C₂₄ alkaryloxy, acyl (including C₂-C₂₄alkylcarbonyl (—CO-alkyl) and C₆-C₂₄ arylcarbonyl (—CO-aryl)), acyloxy(—O-acyl, including C₂-C₂₄ alkylcarbonyloxy (—O—CO-alkyl) and C₆-C₂₄arylcarbonyloxy (—O—CO-aryl)), C₁-C₂₄ alkoxycarbonyl (—(CO)—O-alkyl),C₆-C₂₄ aryloxycarbonyl (—(CO)—O-aryl), halocarbonyl (—CO)—X where X ishalo), C₂-C₂₄ alkylcarbonato (—O—(CO)—O-alkyl), C₆-C₂₄ arylcarbonato(—O—(CO)—O-aryl), carboxy (—COOH), carboxylato (—COO³¹), carbamoyl(—(CO)—NH₂), mono-(C₁-C₂₄ alkyl)-substituted carbamoyl (—(CO)—NH(C₁-C₂₄alkyl)), di-(C₁-C₂₄ alkyl)-substituted carbamoyl (—(CO)—N(C₁-C₂₄alkyl)₂), mono-(C₁-C₂₄ haloalkyl)-substituted carbamoyl (—(CO)—NH(C₁-C₂₄alkyl)), di-(C₁-C₂₄ haloalkyl)-substituted carbamoyl (—(CO)—N(C₁-C₂₄alkyl)₂), mono-(C₅-C₂₄ aryl)-substituted carbamoyl (—(CO)—NH-aryl),di-(C₅-C₂₄ aryl)-substituted carbamoyl (—(CO)—N(C₅-C₂₄ aryl)₂),di-N—(C₁-C₂₄ alkyl),N—(C₅-C₂₄ aryl)-substituted carbamoyl, thiocarbamoyl(—(CS)—NH₂), mono-(C₁-C₂₄ alkyl)-substituted thiocarbamoyl(—(CO)—NH(C₁-C₂₄ alkyl)), di-(C₁-C₂₄ alkyl)-substituted thiocarbamoyl(—(CO)—N(C₁-C₂₄ alkyl)₂), mono-(C₅-C₂₄ aryl)-substituted thiocarbamoyl(—(CO)—NH-aryl), di-(C₅-C₂₄ aryl)-substituted thiocarbamoyl(—(CO)—N(C₅-C₂₄ aryl)₂), di-N—(C₁-C₂₄ alkyl),N—(C₅-C₂₄ aryl)-substitutedthiocarbamoyl, carbamido (—NH—(CO)—NH₂), cyano(—C═N), cyanato (—O—C═N),thiocyanato (—S—C═N), formyl (—(CO)—H), thioformyl (—(CS)—H), amino(—NH₂), mono-(C₁-C₂₄ alkyl)-substituted amino, di-(C₁-C₂₄alkyl)-substituted amino, mono-(C₅-C₂₄ aryl)-substituted amino,di-(C₅-C₂₄ aryl)-substituted amino, C₂-C₂₄ alkylamido (—NH—(CO)-alkyl),C₆-C₂₄ arylamido (—NH—(CO)-aryl), imino (—CR═NH where R=hydrogen, C₁-C₂₄alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), C₂-C₂₀alkylimino (—CR═N(alkyl), where R=hydrogen, C₁-C₂₄ alkyl, C₅-C₂₄ aryl,C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), arylimino (—CR═N(aryl), whereR=hydrogen, C₁-C₂₀ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl,etc.), nitro (-NO2), nitroso (—NO), sulfo (—SO₂—OH), sulfonato(—SO₂—O⁻), C₁-C₂₄ alkylsulfanyl (—S-alkyl; also termed “alkylthio”),C₅-C₂₄ arylsulfanyl (—S-aryl; also termed “arylthio”), C₁-C₂₄alkylsulfinyl (—(SO)-alkyl), C₅-C₂₄ arylsulfinyl (—(SO)-aryl), C₁-C₂₄alkylsulfonyl (—SO₂-alkyl), C₁-C₂₄ monoalkylaminosulfonyl-SO₂—N(H)alkyl), C₁-C₂₄ dialkylaminosulfonyl —SO₂—N(alkyl)₂, C₅-C₂₄ arylsulfonyl(—SO₂-aryl), boryl (—BH₂), borono (—B(OH)₂), boronato (—B(OR)₂ where Ris alkyl or other hydrocarbyl), phosphono (—P(O)(OH)₂), phosphonato(—P(O)(O⁻)₂), phosphinato (—P(O)(O⁻)), phospho (—PO₂), and phosphino(—PH₂); and the hydrocarbyl moieties C₁-C₂₄ alkyl (preferably C₁-C₁₂alkyl, more preferably C₁-C₆ alkyl), C₂-C₂₄ alkenyl (preferably C₂-C₁₂alkenyl, more preferably C₂-C₆ alkenyl), C₂-C₂₄ alkynyl (preferablyC₂-C₁₂ alkynyl, more preferably C₂-C₆ alkynyl), C₅-C₂₄ aryl (preferablyC₅-C₁₄ aryl), C₆-C₂₄ alkaryl (preferably C₆-C₁₆ alkaryl), and C₆-C₂₄aralkyl (preferably C₆-C₁₆ aralkyl).

By “functionalized” as in “functionalized hydrocarbyl,” “functionalizedalkyl,” “functionalized olefin,” “functionalized cyclic olefin,” and thelike, is meant that in the hydrocarbyl, alkyl, olefin, cyclic olefin, orother moiety, at least one hydrogen atom bound to a carbon (or other)atom is replaced with one or more functional groups such as thosedescribed hereinabove. The term “functional group” is meant to includeany functional species that is suitable for the uses described herein.In particular, as used herein, a functional group would necessarilypossess the ability to react with or bond to corresponding functionalgroups on a substrate surface.

In addition, the aforementioned functional groups may, if a particulargroup permits, be further substituted with one or more additionalfunctional groups or with one or more hydrocarbyl moieties such as thosespecifically enumerated above. Analogously, the above-mentionedhydrocarbyl moieties may be further substituted with one or morefunctional groups or additional hydrocarbyl moieties such as thosespecifically enumerated.

“Optional” or “optionally” means that the subsequently describedcircumstance may or may not occur, so that the description includesinstances where the circumstance occurs and instances where it does not.For example, the phrase “optionally substituted” means that anon-hydrogen substituent may or may not be present on a given atom, and,thus, the description includes structures wherein a non-hydrogensubstituent is present and structures wherein a non-hydrogen substituentis not present.

Controlling the Formation of the (E)-Isomer in Metathesis Reactions

Olefin metathesis is a powerful method for the synthesis of C═C bonds ina variety of synthetic contexts, including organic synthesis, polymerchemistry, materials science, and biochemistry. Control of olefingeometry is frequently crucial to controlling the properties of amolecule, leading synthetic chemists to develop numerous stereoselectiveolefination methods. While recent advances have uncovered a family of(Z)-selective olefin metathesis catalysts, complexes capable ofkinetically controlled (E)-selective cross metathesis remain elusive(Furstner, A., Teaching Metathesis “Simple” Stereochemistry. Science2013, 341, 1357). As a consequence, chemists have relied on the rapidrates of equilibration during olefin metathesis and the thermodynamicstability of (E) olefins to generate (E) products. Scheme 1a and Scheme1b show the (E/Z) selectivity in olefin metathesis by second generationGrubbs catalysts.

However, in many contexts, the relative energies of (E) and (Z) isomersare similar, resulting in mixtures as shown in Scheme 1c (Furstner, A.;Dierkes, T.; Thiel, O. R.; Blanda, G., Total synthesis of(−)-salicylihalamide. Chem. Eur. J. 2001, 7, 5286-5298).

Indirect solutions to this problem have required alkynemetathesis/semi-reduction, ((a) Furstner, A.; Radkowski, K., A chemo-and stereoselective reduction of cycloalkynes to (E) cycloalkenes. Chem.Commun. 2002, 2182-2183; (b) Lehr, K.; Mariz, R.; Leseurre, L.; Gabor,B.; Fuerstner, A., Total Synthesis of Tulearin C. Angew. Chem., Int. Ed.2011, 50, 11373-11377); temporary auxiliary groups, or conformationalcontrol, (Matsui, R.; Seto, K.; Fujita, K.; Suzuki, T.; Nakazaki, A.;Kobayashi, S., Unusual E-Selective Ring-Closing Metathesis To FormEight-Membered Rings. Angew. Chem., Int. Ed. 2010, 49, 10068-10073),which complicate the synthetic sequence and lack generality.

In addition to the practical advantages, designing an (E)-selectivemetathesis catalyst presents a major intellectual challenge. Thefeatures of a (Z)-selective catalyst were straightforward but difficultto execute. For a (Z)-selective system it is apparent that one side ofthe metallacyclic intermediate must be sterically blocked to push allsubstituents to the same side of the metallacycle as shown in Scheme 2.

The development of (Z)-selective ruthenium catalysts (a) Endo, K.;Grubbs, R. H., Chelated ruthenium catalysts for (Z)-selective olefinmetathesis. J. Am. Chem. Soc. 2011, 133, 8525-8527; (b) Keitz, B. K.;Endo, K.; Herbert, M. B.; Grubbs, R. H., (Z)-selective homodimerizationof terminal olefins with a ruthenium metathesis catalyst. J. Am. Chem.Soc. 2011, 133, 9686-9688; (c) Keitz, B. K.; Endo, K.; Patel, P. R.;Herbert, M. B.; Grubbs, R. H., Improved ruthenium catalysts for(Z)-selective olefin metathesis. J. Am. Chem. Soc. 2012, 134, 693-699,required an initially unexpected cyclometalated architecture thatimposed a preference for the formation of side bound metallacycles(rather than bottom-bound metallacycles normally found in non-chelatedcatalysts). As illustrated in Scheme 2, the side-bound intermediatesplace the metallacycle underneath the N substituents of theN-heterocyclic carbene (NHC) (Liu, P.; Xu, X.; Dong, X.; Keitz, B. K.;Herbert, M. B.; Grubbs, R. H.; Houk, K. N.), (Z) Selectivity in olefinmetathesis with chelated Ru catalysts: computational studies ofmechanism and selectivity (J. Am. Chem. Soc. 2012, 134, 1464-1467). Weextensively investigated models for (E) selectivity using side-boundmodels, however, our efforts proved unfruitful, presumably due tosterically disfavor between substituent in metallacycle and bulky ligand(the right model in Scheme 2).

Therefore, we will explore this chemistry utilizing bottom-boundapproaches. For an (E)-selective catalyst, the steric requirement ismuch more difficult (although the preference for (E) is alreadypresent). Also, two different designs maybe required for the standardring opening cross metathesis (ROCM) and simple cross metathesis (CM) asshown in Scheme 3.

In the ROCM reaction, (substituents at C2 and C3 of metallacycle must becis) the stereochemistry of the product is controlled by the transstereochemistry of substituents at the C2 and C4. In the crossmetathesis reactions, the stereochemistry is controlled by the transrelationship of substituents at the C3 and C4 positions and requires athird steric block that pushes the substituent at C3 to a position transto the substituent at the C2 and C4 positions.

Exploratory studies have identified a promising candidate for akinetically controlled (E)-selective metathesis catalyst. The inherentlyreversible nature of olefin metathesis often inhibits the directmeasurement of (E/Z) geometries, i.e., secondary metathesis. Thus, thecompetency for (E)-selectivity was probed by reacting well-establishedRu catalysts with 2,3-dihydrofuran. This reaction is irreversible underthe given conditions and models the key step in ring opening crossmetathesis. As illustrated in Table 1, the new ruthenium catalyst(3)-rac yields its corresponding Fischer carbene complex with an (E/Z)ratio of >20:1, which is significantly higher than ratio given by 1^(st)and 2^(nd) generation Grubbs catalysts, C823 (1) and C848 (2). Sinceunder ambient reaction conditions, Fischer carbenes do not undergofurther metathesis reactions, this reaction measures the inherent (E/Z)selectivity of a given catalyst. The mono ortho substituents on (3)-racappear to provide the steric block for the C2 and C4 positions asdescribed in Scheme 3. Furthermore, zero substitution on an orthoposition can also allow the substituent at the C4 to be trans to the C2position. FIG. 1 shows the ¹H-NMR array experiment in the ROCM of2,3-dihydrofuran with catalyst (3)-rac.

TABLE 1 (E/Z) Ratio metathesis of 2,3-dihydrofuran for rutheniumcatalysts

Ru-catalyst

E/Z ratio 1

4:1 C823 2

6:1 C848 3

>20:1    (3)-rac 4

~8:1   C849 5

3:1 C933 6

~9:1   C822

Metal Carbene Olefin Metathesis Catalysts

A metal carbene olefin metathesis catalyst that may be used in theinvention disclosed herein, is preferably a Group 8 transition metalcomplex having the structure of Formula (I):

in which:

M is a Group 8 transition metal;

L¹ is an N-heterocyclic carbene ligand (i.e., NHC ligand) having thestructure of Formula (II) or of Formula (III):

R^(V1), R^(V2), R^(V3), R^(V4), and R^(V5) are independently hydrogen,substituted branched C₁-C₆ alkyl, C₄-C₁₀ cycloalkyl, substituted C₄-C₁₀cycloalkyl, C₄-C₁₀ heteroatom-containing cycloalkyl, substituted C₄-C₁₀heteroatom-containing cycloalkyl, C₅-C₁₄ aryl, substituted C₅-C₁₄ aryl;

R¹¹, R¹², R^(11a), R^(12a) are independently hydrogen, C₁-C₁₂ alkyl,substituted C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy, substituted C₁-C₁₂ alkoxy,C₅-C₁₄ aryl, substituted C₁-C14 aryl, or halide; and at least one ofR^(V1), R^(V2), R^(V3), R^(V4,) or R^(V5) is represented by a group suchas:

“a” represents 0, 1, 2, 3, 4, or 5;

R is substituted C₁-C₆ alkyl, C₁-C₆ alkyl, substituted C₃-C₁₀cycloalkyl, C₃-C₁₀ cycloalkyl, or halogen;

L² and L³ are neutral electron donor ligands;

n is 0 or 1, such that L³ may or may not be present;

m is 0, 1, or 2;

k is 0 or 1;

X¹ and X² are anionic ligands; and

R¹ and R² are independently selected from hydrogen, hydrocarbyl,substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substitutedheteroatom-containing hydrocarbyl, and functional groups, wherein anytwo or more of X¹, X², L¹, L², L³, R¹, and R² can be taken together toform one or more cyclic groups, and further wherein any one or more ofX¹, X², L¹, L², L³, R¹, and R² may be attached to a support.

Additionally, in Formula (I) one or both of R¹ and R² may have thestructure —(W)_(n)—U⁺V³¹ , in which W is selected from hydrocarbylene,substituted hydrocarbylene, heteroatom-containing hydrocarbylene, orsubstituted heteroatom-containing hydrocarbylene; U is a positivelycharged Group 15 or Group 16 element substituted with hydrogen,hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl,or substituted heteroatom-containing hydrocarbyl; V is a negativelycharged counterion; and n is zero or 1. Furthermore, R¹ and R² may betaken together to form an indenylidene moiety, preferably aphenylindenylidene moiety.

Preferred catalysts contain Ru or Os as the Group 8 transition metal,with Ru particularly preferred.

Numerous embodiments of the catalysts useful in the reactions disclosedherein are described in more detail infra. For the sake of convenience,the catalysts are described in groups, but it should be emphasized thatthese groups are not meant to be limiting in any way. That is, any ofthe catalysts useful in the invention may fit the description of morethan one of the groups described herein.

For the first group of catalysts, n is 0, and L² is selected fromphosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite,arsine, stibine, ether, (including cyclic ethers), amine, amide, imine,sulfoxide, carboxyl, nitrosyl, pyridine, substituted pyridine,imidazole, substituted imidazole, pyrazine, substituted pyrazine andthioether. Exemplary ligands are trisubstituted phosphines. Preferredtrisubstituted phosphines are of the formula PR^(H1)R^(H2)R^(H3), whereR^(H1), R^(H2), and R^(H3) are each independently substituted orunsubstituted aryl or C₁-C₁₀ alkyl, particularly primary alkyl,secondary alkyl, or cycloalkyl. In the most preferred embodiment, L² isselected from the group consisting of trimethylphosphine (PMe₃),triethylphosphine (PEt₃), tri-n-butylphosphine (PBu₃),tri(ortho-tolyl)phosphine (P-o-tolyl₃), tri-tert-butylphosphine(P-tert-Bu₃), tricyclopentylphosphine (PCyclopentyl₃),tricyclohexylphosphine (PCy₃), triisopropylphosphine (P-i-Pr₃),trioctylphosphine (POct₃), triisobutylphosphine, (P-i-Bu₃),triphenylphosphine (PPh₃), tri(pentafluorophenyl)phosphine (P(C₆F₅)₃),methyldiphenylphosphine (PMePh₂), dimethylphenylphosphine (PMe₂Ph), anddiethylphenylphosphine (PEt₂Ph). Alternatively, L² may be selected fromphosphabicycloalkane (e.g., monosubstituted9-phosphabicyclo-[3.3.1]nonane, or monosubstituted9-phosphabicyclo[4.2.1]nonane] such as cyclohexylphoban,isopropylphoban, ethylphoban, methylphoban, butylphoban, pentylphobanand the like).

X¹ and X² are anionic ligands, and may be the same or different, or arelinked together to form a cyclic group, typically although notnecessarily a five- to eight-membered ring. In preferred embodiments, X¹and X² are each independently hydrogen, halide, or one of the followinggroups: C₁-C₂₀ alkyl, C₅-C₂₄ aryl, C₁-C₂₀ alkoxy, C₅-C₂₄ aryloxy, C₂-C₂₀alkoxycarbonyl, C₆-C₂₄ aryloxycarbonyl, C₂-C₂₄ acyl, C₂-C₂₄ acyloxy,C₁-C₂₀ alkylsulfonato, C₅-C₂₄ arylsulfonato, C₁-C₂₀ alkylsulfanyl,C₅-C₂₄ arylsulfanyl, C₁-C₂₀ alkylsulfinyl, NO₃, —N═C═O, —N═C═S, orC₅-C₂₄ arylsulfinyl. Optionally, X¹ and X² may be substituted with oneor more moieties selected from C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy, C₅-C₂₄ aryl,and halide, which may, in turn, with the exception of halide, be furthersubstituted with one or more groups selected from halide, C₁-C₆ alkyl,C₁-C₆ alkoxy, and phenyl. In more preferred embodiments, X¹ and X² arehalide, benzoate, C₂-C₆ acyl, C₂-C₆ alkoxycarbonyl, C₁-C₆ alkyl,phenoxy, C₁-C₆ alkoxy, C₁-C₆ alkylsulfanyl, aryl, or C₁-C₆alkylsulfonyl. In even more preferred embodiments, X¹ and X² are eachhalide, CF₃CO₂, CH₃CO₂, CFH₂CO₂, (CH₃)₃CO, (CF₃)₂(CH₃)CO, (CF₃)(CH₃)₂CO,PhO, MeO, EtO, tosylate, mesylate, or trifluoromethane-sulfonate. In themost preferred embodiments, X¹ and X² are each chloride.

R¹ and R² are independently selected from hydrogen, hydrocarbyl (e.g.,C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₅-C₂₄ aryl, C₆-C₂₄alkaryl, C₆-C₂₄ aralkyl, etc.), substituted hydrocarbyl (e.g.,substituted C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₅-C₂₄ aryl,C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), heteroatom-containing hydrocarbyl(e.g., heteroatom-containing C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀alkynyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), andsubstituted heteroatom-containing hydrocarbyl (e.g., substitutedheteroatom-containing C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl,C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), and functionalgroups. R¹ and R² may also be linked to form a cyclic group, which maybe aliphatic or aromatic, and may contain substituents and/orheteroatoms. Generally, such a cyclic group will contain 4 to 12,preferably 5, 6, 7, or 8 ring atoms.

In preferred catalysts, R¹ is hydrogen and R² is selected from C₁-C₂₀alkyl, C₂-C₂₀ alkenyl, and C₅-C₂₄ aryl, more preferably C₁-C₆ alkyl,C₂-C₆ alkenyl, and C₅-C₁₄ aryl. Still more preferably, R² is phenyl,vinyl, methyl, isopropyl, or t-butyl, optionally substituted with one ormore moieties selected from C₁-C₆ alkyl, C₁-C₆ alkoxy, phenyl, and afunctional group Fn as defined earlier herein. Most preferably, R² isphenyl or vinyl substituted with one or more moieties selected frommethyl, ethyl, chloro, bromo, iodo, fluoro, nitro, dimethylamino,methyl, methoxy, and phenyl. Optimally, R² is phenyl or —CH=C(CH₃)_(2.)

Any two or more (typically two, three, or four) of X¹, X², L¹, L², L³,R¹, and R² be taken together to form a cyclic group, including bidentateor multidentate ligands, as disclosed, for example, in U.S. Pat. No.5,312,940, the disclosure of which is incorporated herein by reference.When any of X¹, X², L¹, L², L³, R¹, and R² are linked to form cyclicgroups, those cyclic groups may contain 4 to 12, preferably 4, 5, 6, 7,or 8 atoms, or may comprise two or three of such rings, which may beeither fused or linked. The cyclic groups may be aliphatic or aromatic,and may be heteroatom-containing and/or substituted. The cyclic groupmay, in some cases, form a bidentate ligand or a tridentate ligand.Examples of bidentate ligands include, but are not limited to,bisphosphines, dialkoxides, alkyldiketonates, and aryldiketonates.

The Group 8 transition metal complex having the structure of Formula (I)may be in a racemic isomeric form, a meso isomeric form, or a mixture ofthe racemic and meso isomeric forms.

In another embodiment, metal carbene olefin metathesis catalysts of theinvention comprise a Group 8 transition metal complex having thestructure of Formula (IV):

wherein:

M is Ru or Os;

R^(V1), R^(V2), R^(V3), R^(V4), and R^(V5) are independently hydrogen,substituted branched C₁-C₆ alkyl, C₄-C₁₀ cycloalkyl, substituted C₄-C₁₀cycloalkyl, C₄-C₁₀ heteroatom-containing cycloalkyl, substituted C₄-C₁₀heteroatom-containing cycloalkyl, C₅-C₁₄ aryl, substituted C₅-C₁₄ aryl;

R¹¹, R¹², R^(11a), and R^(12a) are independently hydrogen, C₁-C₁₂ alkyl,substituted C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy, substituted C₁-C₁₂ alkoxy,C₅-C₁₄ aryl, substituted C₅-C14 aryl, or halide;

X¹ and X² are independently halogen;

L² and L³ are neutral electron donor ligands, wherein L² and/or L³ maybe linked with R¹ or R² to form one or more cyclic groups;

n is 0 or 1, such that L³ may or may not be present;

m is 0, 1, or 2;

k is 0 or 1;

R¹ and R² are independently selected from hydrogen, hydrocarbyl,substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substitutedheteroatom-containing hydrocarbyl, and functional groups, where R¹ andR² may be linked together to form a ring (for example C₄-C₁₀ ring, orC₅-C₆ ring) that may be substituted or unsubstituted, saturated orunsaturated and may be fused or linked to a further ring (for example aC₄-C₁₀ ring or a C₅-C₆ ring); and at least one of R^(V1), R^(V2),R^(V3), R^(V4), or R^(V5) is represented by a group such as:

“a” represents 0, 1, 2, 3, 4, or 5; and

R is substituted C₁-C₆ alkyl, C₁-C₆ alkyl, substituted C₃-C₁₀cycloalkyl, C₃-C₁₀ cycloalkyl, or halogen.

The Group 8 transition metal complex having the structure of Formula(IV) may be in a racemic isomeric form, a meso isomeric form, or amixture of the racemic and meso isomeric forms.

In another embodiment, metal carbene olefin metathesis catalysts of theinvention comprise a Group 8 transition metal complex having thestructure of Formula (V):

wherein:

M is Ru or Os;

R^(V1), R^(V2), R^(V3), R^(V4), and R^(V5) are independently hydrogen,substituted branched C₁-C₆ alkyl, C₄-C₁₀ cycloalkyl, substituted C₄-C₁₀cycloalkyl, C₄-C₁₀ heteroatom-containing cycloalkyl, substituted C₄-C₁₀heteroatom-containing cycloalkyl, C₅-C₁₄ aryl, substituted C₅-C₁₄ aryl;

R¹¹ and R¹² are independently hydrogen, C₁-C₁₂ alkyl, substituted C₁-C₁₂alkyl, C₁-C₁₂ alkoxy, substituted C₁-C₁₂ alkoxy, C₅-C₁₄ aryl,substituted C₅-C₁₄ aryl, or halide;

X¹ and X² are independently halogen;

L² and L³ are neutral electron donor ligands, wherein L² and/or L³ maybe linked with R¹ or R² to form one or more cyclic groups;

n is 0 or 1, such that L³ may or may not be present;

m is 0, 1, or 2;

k is 0 or 1;

R¹ and R² are independently selected from hydrogen, hydrocarbyl,substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substitutedheteroatom-containing hydrocarbyl, and functional groups, where R¹ andR² may be linked together to form a ring (for example C₄-C₁₀ ring, orC₅-C₆ ring) that may be substituted or unsubstituted, saturated orunsaturated and may be fused or linked to a further ring (for example aC₄-C₁₀ ring or a C₅-C₆ ring); and

at least one of R^(V1), R^(V2), R^(V3), R^(V4), or R^(V5) is representedby a group such as:

“a” represents 0, 1, 2, 3, 4, or 5; and

R is substituted C₁-C₆ alkyl, C₁-C₆ alkyl, substituted C₃-C₁₀cycloalkyl, C₃-C₁₀ cycloalkyl, or halogen.

The Group 8 transition metal complex having the structure of Formula (V)may be in a racemic isomeric form, a meso isomeric form, or a mixture ofthe racemic and meso isomeric forms.

In a second group of catalysts having the structure of Formula (I),wherein M, m, n, X¹, X², R¹, and R² are as defined for the first groupof catalysts, L¹ is of Formula (II) or of Formula (III) and L² and L³are weakly coordinating neutral electron donor ligands in the form ofoptionally substituted heterocyclic groups. Again, n is zero or 1, suchthat L³ may or may not be present. Generally, in the second group ofcatalysts, L² and L³ are optionally substituted five- or six-memberedmonocyclic groups containing 1 to 4, preferably 1 to 3, most preferably1 to 2 heteroatoms, or are optionally substituted bicyclic or polycyclicstructures composed of 2 to 5 such five- or six-membered monocyclicgroups. If the heterocyclic group is substituted, it should not besubstituted on a coordinating heteroatom, and any one cyclic moietywithin a heterocyclic group will generally not be substituted with morethan 3 substituents.

For the second group of catalysts, examples of L² and L³ include,without limitation, heterocycles containing nitrogen, sulfur, oxygen, ora mixture thereof.

Examples of nitrogen-containing heterocycles appropriate for L² and L³include pyridine, bipyridine, pyridazine, pyrimidine, bipyridamine,pyrazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,3 -triazine, pyrrole,2H-pyrrole, 3H-pyrrole, pyrazole, 2H-imidazole, 1,2,3 -triazole,1,2,4-triazole, indole, 3H-indole, 1H-isoindole, cyclopenta(b)pyridine,indazole, quinoline, bisquinoline, isoquinoline, bisisoquinoline,cinnoline, quinazoline, naphthyridine, piperidine, piperazine,pyrrolidine, pyrazolidine, quinuclidine, imidazolidine, picolylimine,purine, benzimidazole, bisimidazole, phenazine, acridine, and carbazole.Additionally, the nitrogen-containing heterocycles may be optionallysubstituted on a non-coordinating heteroatom with a non-hydrogen substitutent.

Examples of sulfur-containing heterocycles appropriate for L² and L³include thiophene, 1,2-dithiole, 1,3 -dithiole, thiepin,benzo(b)thiophene, benzo(c)thiophene, thionaphthene, dibenzothiophene,2H-thiopyran, 4H-thiopyran, and thioanthrene.

Examples of oxygen-containing heterocycles appropriate for L² and L³include 2H-pyran, 4H-pyran, 2-pyrone, 4-pyrone, 1,2-dioxin, 1,3-dioxin,oxepin, furan, 2H-1-benzopyran, coumarin, coumarone, chromene,chroman-4-one, isochromen- 1 -one, isochromen-3 -one, xanthene,tetrahydrofuran, 1,4-dioxan, and dibenzofuran.

Examples of mixed heterocycles appropriate for L² and L³ includeisoxazole, oxazole, thiazole, isothiazole, 1,2,3-oxadiazole,1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,3,4-oxatriazole,1,2,3,5-oxatriazole, 3H-1,2,3-dioxazole, 3H-1,2-oxathiole,1,3-oxathiole, 4H-1,2-oxazine, 2H-1,3-oxazine, 1,4-oxazine,1,2,5-oxathiazine, o-isooxazine, phenoxazine, phenothiazine,pyrano[3,4-b]pyrrole, indoxazine, benzoxazole, anthranil, andmorpholine.

Preferred L² and L³ ligands are aromatic nitrogen-containing andoxygen-containing heterocycles, and particularly preferred L² and L³ligands are monocyclic N-heteroaryl ligands that are optionallysubstituted with 1 to 3, preferably 1 or 2, substituents. Specificexamples of particularly preferred L² and L³ ligands are pyridine andsubstituted pyridines, such as 3-bromopyridine, 4-bromopyridine, 3,5-dibromopyridine, 2,4,6-tribromopyridine, 2,6-dibromopyridine,3-chloropyridine, 4-chloropyridine, 3,5-dichloropyridine,2,4,6-trichloropyridine, 2,6-dichloropyridine, 4-iodopyridine,3,5-diiodopyridine, 3,5-dibromo-4-methylpyridine,3,5-dichloro-4-methylpyridine, 3,5-dimethyl-4-bromopyridine,3,5-dimethylpyridine, 4-methylpyridine, 3,5-diisopropylpyridine,2,4,6-trimethylpyridine, 2,4,6-triisopropylpyridine,4-(tert-butyl)pyridine, 4-phenylpyridine, 3,5-diphenylpyridine,3,5-dichloro-4-phenylpyridine, and the like.

In general, any substituents present on L² and/or L³ are selected fromhalo, C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, C₁-C₂₀ heteroalkyl,substituted C₁-C₂₀ heteroalkyl, C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl,C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, C₆-C₂₄ alkaryl,substituted C₆-C₂₄ alkaryl, C₆-C₂₄ heteroalkaryl, substituted C₆-C₂₄heteroalkaryl, C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, C₆-C₂₄heteroaralkyl, substituted C₆-C₂₄ heteroaralkyl, and functional groups,with suitable functional groups including, without limitation, C₁-C₂₀alkoxy, C₅-C₂₄ aryloxy, C₂-C₂₀ alkylcarbonyl, C₆-C₂₄ arylcarbonyl,C₂-C₂₀ alkylcarbonyloxy, C₆-C₂₄ arylcarbonyloxy, C₂-C₂₀alkoxycarbonyl,C₆-C₂₄ aryloxycarbonyl, halocarbonyl, C₂-C₂₀ alkylcarbonato, C₆-C₂₄arylcarbonato, carboxy, carboxylato, carbamoyl, mono-(C₁-C₂₀alkyl)-substituted carbamoyl, di-(C₁-C₂₀ alkyl)-substituted carbamoyl,di-N—(C₁-C₂₀ alkyl), N—(C₅-C₂₄ aryl)-substituted carbamoyl, mono-(C₅-C₂₄aryl)-substituted carbamoyl, di-(C₆-C₂₄ aryl)-substituted carbamoyl,thiocarbamoyl, mono-(C₁-C₂₀ alkyl)-substituted thiocarbamoyl, di-(C₁-C₂₀alkyl)-substituted thiocarbamoyl, di-N—(C₁-C₂₀ alkyl)-N—(C₆-C₂₄aryl)-substituted thiocarbamoyl, mono-(C₆-C₂₄ aryl)-substitutedthiocarbamoyl, di-(C₆-C₂₄ aryl)-substituted thiocarbamoyl, carbamido,formyl, thioformyl, amino, mono-(C₁-C₂₀ alkyl)-substituted amino,di-(C₁-C₂₀ alkyl)-substituted amino, mono-(C₅-C₂₄ aryl)-substitutedamino, di-(C₅-C₂₄ aryl)-substituted amino, di-N—(C₁-C₂₀ alkyl),N—(C₅-C₂₄aryl)-substituted amino, C₂-C₂₀ alkylamido, C₆-C₂₄ arylamido, imino,C₁-C₂₀ alkylimino, C₅-C₂₄ arylimino, nitro, and nitroso. In addition,two adjacent substituents may be taken together to form a ring,generally a five- or six-membered alicyclic or aryl ring, optionallycontaining 1 to 3 heteroatoms and 1 to 3 substituents as above.

Preferred substituents on L² and L³ include, without limitation, halo,C₁-C₁₂ alkyl, substituted C₁-C₁₂ alkyl, C₁-C₁₂ heteroalkyl, substitutedC₁-C₁₂ heteroalkyl, C₅-C₁₄ aryl, substituted C₅-C₁₄ aryl, C₅-C₁₄heteroaryl, substituted C₅-C₁₄ heteroaryl, C₆-C₁₆ alkaryl, substitutedC₆-C₁₆ alkaryl, C₆-C₁₆ heteroalkaryl, substituted C₆-C₁₆ heteroalkaryl,C₆-C₁₆ aralkyl, substituted C₆-C₁₆ aralkyl, C₆-C₁₆ heteroaralkyl,substituted C₆-C₁₆ heteroaralkyl, C₁-C₁₂ alkoxy, C₅-C₁₄ aryloxy, C₂-C₁₂alkylcarbonyl, C₆-C₁₄ arylcarbonyl, C₂-C₁₂ alkylcarbonyloxy, C₆-C₁₄arylcarbonyloxy, C₂-C₁₂ alkoxycarbonyl, C₆-C₁₄ aryloxycarbonyl,halocarbonyl, formyl, amino, mono-(C₁-C₁₂ alkyl)-substituted amino,di-(C₁-C₁₂ alkyl)-substituted amino, mono-(C₅-C₁₄ aryl)-substitutedamino, di-(C₅-C₁₄ aryl)-substituted amino, and nitro.

Of the foregoing, the most preferred substituents are halo, C₁-C₆ alkyl,C₁-C₆ haloalkyl, C₁-C₆ alkoxy, phenyl, substituted phenyl, formyl,N,N-di(C₁-C₆ alkyl)amino, nitro, and nitrogen heterocycles as describedabove (including, for example, pyrrolidine, piperidine, piperazine,pyrazine, pyrimidine, pyridine, pyridazine, etc.).

Complexes wherein Y is coordinated to the metal are examples of a thirdgroup of metal carbene olefin metathesis catalysts, and are commonlycalled “Grubbs-Hoveyda” catalysts. Grubbs-Hoveyda metathesis-activemetal carbene complexes may be described by the Formula (VI):

wherein:

M is a Group 8 transition metal, particularly Ru or Os, or, moreparticularly, Ru;

L¹ is of Formula (II) or of Formula (III), and, X¹ and X² are aspreviously defined herein for the first and second groups of metalcarbene olefin metathesis catalysts;

Y is a heteroatom selected from N, O, S, and P; preferably Y is O or N;

R⁵, R⁶, R⁷, and R⁸ are each, independently, selected from the groupconsisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl,heteroalkyl, heteroatom containing alkenyl, heteroalkenyl, heteroaryl,alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino,alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl,alkyl sulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl,perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano,isocyanate, hydroxyl, ester, ether, amine, imine, amide,halogen-substituted amide, trifluoroamide, sulfide, disulfide,sulfonate, carbamate, silane, siloxane, phosphine, phosphate, borate,or-A-Fn, wherein “A” and Fn have been defined above; and any combinationof Y, Z, R⁵, R⁶, R⁷, and R⁸ can be linked to form one or more cyclicgroups;

n is 0, 1, or 2, such that n is 1 for the divalent heteroatoms O or S,and n is 2 for the trivalent heteroatoms N or P; and

Z is a group selected from hydrogen, alkyl, aryl, functionalized alkyl,functionalized aryl where the functional group(s) may independently beone or more or the following: alkoxy, aryloxy, halogen, carboxylic acid,ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether,amine, imine, amide, trifluoroamide, sulfide, disulfide, carbamate,silane, siloxane, phosphine, phosphate, or borate; methyl, isopropyl,sec-butyl, t-butyl, neopentyl, benzyl, phenyl and trimethylsilyl.Additionally, R⁵, R⁶, R⁷, R⁸, and Z may independently be thioisocyanate,cyanato, or thiocyanato.

The Group 8 transition metal complex having the structure of Formula(VI) may be in a racemic isomeric form, a meso isomeric form, or amixture of the racemic and meso isomeric forms.

In another embodiment, metal carbene olefin metathesis catalysts of theinvention comprise a Group 8 transition metal complex having thestructure of Formula (VII):

wherein:

M is Ru or Os;

R^(V1), R^(V2), R^(V3), R^(V4), and R^(V5) are independently hydrogen,substituted branched C₁-C₆ alkyl, C₄-C₁₀ cycloalkyl, substituted C₄-C₁₀cycloalkyl, C₄-C₁₀ heteroatom-containing cycloalkyl, substituted C₄-C₁₀heteroatom-containing cycloalkyl, C₅-C₁₄ aryl, substituted C₅-C₁₄ aryl;

R¹¹, R¹², R^(11a), and R^(12a) are independently hydrogen, C₁-C₁₂ alkyl,substituted C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy, substituted C₁-C₁₂ alkoxy,C₅-C₁₄ aryl, substituted C₅-C₁₄ aryl, or halide;

X¹ and X² are independently halogen;

Y is a heteroatom selected from N, O, S, and P; preferably Y is O or N;

R⁵, R⁶, R⁷, and R⁸ are each, independently, selected from the groupconsisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl,heteroalkyl, heteroatom containing alkenyl, heteroalkenyl, heteroaryl,alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino,alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl,alkyl sulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl,perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano,isocyanate, hydroxyl, ester, ether, amine, imine, amide,halogen-substituted amide, trifluoroamide, sulfide, disulfide,sulfonate, carbamate, silane, siloxane, phosphine, phosphate, borate,or-A-Fn, wherein “A” and Fn have been defined above; and any combinationof Y, Z, R⁵, R⁶, R⁷, and R⁸ can be linked to form one or more cyclicgroups;

n is 0, 1, or 2, such that n is 1 for the divalent heteroatoms O or S,and n is 2 for the trivalent heteroatoms N or P; and

Z is a group selected from hydrogen, alkyl, aryl, functionalized alkyl,functionalized aryl where the functional group(s) may independently beone or more or the following: alkoxy, aryloxy, halogen, carboxylic acid,ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether,amine, imine, amide, trifluoroamide, sulfide, disulfide, carbamate,silane, siloxane, phosphine, phosphate, or borate; methyl, isopropyl,sec-butyl, t-butyl, neopentyl, benzyl, phenyl and trimethylsilyl; and

at least one of R^(V1), R^(V2), R^(V3), R^(V4), or R^(V5) is representedby a group such as:

“a” represents 0, 1, 2, 3, 4, or 5; and

R is substituted C₁-C₆ alkyl, C₁-C₆ alkyl, substituted C₃-C₁₀cycloalkyl, C₃-C₁₀ cycloalkyl, or halogen.

The Group 8 transition metal complex having the structure of Formula(VII) may be in a racemic isomeric form, a meso isomeric form, or amixture of the racemic and meso isomeric forms.

In another embodiment, metal carbene olefin metathesis catalysts of theinvention comprise a Group 8 transition metal complex having thestructure of Formula (VII), wherein:

M is Ru;

R^(V1), R^(V2), R^(V3), R^(V4), and R^(V5) are independently hydrogen,substituted branched C₁-C₆ alkyl;

R¹¹, R¹², R^(11a), and R^(12a) are independently hydrogen, C₁-C₁₂ alkyl;

X¹ and X² are independently chloride;

Y is O or N;

R⁵, R⁶, R⁷, and R⁸ are each, independently, selected from the groupconsisting of hydrogen, halogen, alkyl;

n is 1 or 2; and

Z is a group selected from hydrogen and alkyl; and

at least one of R^(V1), R^(V2), R^(V3), R^(V4), or R^(V5) is representedby a group such as:

“a” represents 0, 1, 2, 3, 4, or 5; and

R is substituted C₁-C₆ alkyl, C₁-C₆ alkyl, substituted C₃-C₁₀cycloalkyl, C₃-C₁₀ cycloalkyl, or halogen.

In another embodiment, metal carbene olefin metathesis catalysts of theinvention comprise a Group 8 transition metal complex having thestructure of Formula (VII):

wherein:

M is Ru;

R^(V1), R^(V2), R^(V3), and R^(V4) are independently hydrogen;

R¹¹, R¹² , R^(11a), and R^(12a) are independently hydrogen;

X¹ and X² are independently chloride;

Y is O;

R⁵, R⁶, R⁷, and R⁸ are each hydrogen;

n is 1;

Z is alkyl;

R^(V5) is represented by

and

“a” represents 0.

Examples of complexes comprising Grubbs-Hoveyda ligands suitable in theinvention include:

wherein: L¹ is of Formula (II) or of Formula (III) and, X¹, X², and Mare as described for any of the other groups of catalysts. Suitablechelating carbenes and carbene precursors are further described byPederson et al. (U.S. Pat. Nos. 7,026,495 and 6,620,955, the disclosuresof both of which are incorporated herein by reference) and Hoveyda etal. (U.S. Pat. No. 6,921,735 and WO0214376, the disclosures of both ofwhich are incorporated herein by reference).

In addition to the metal carbene olefin metathesis catalysts that havethe structure of Formula (I), as described above, other transition metalcarbene complexes include, but are not limited to:

neutral ruthenium or osmium metal carbene complexes containing metalcenters that are formally in the +2 oxidation state, have an electroncount of 16, are penta-coordinated, and are of the general Formula(VIII);

neutral ruthenium or osmium metal carbene complexes containing metalcenters that are formally in the +2 oxidation state, have an electroncount of 18, are hexa-coordinated, and are of the general Formula (IX);

cationic ruthenium or osmium metal carbene complexes containing metalcenters that are formally in the +2 oxidation state, have an electroncount of 14, are tetra-coordinated, and are of the general Formula (X);and

cationic ruthenium or osmium metal carbene complexes containing metalcenters that are formally in the +2 oxidation state, have an electroncount of 14 or 16, are tetra-coordinated or penta-coordinated,respectively, and are of the general Formula (XI):

wherein:

M, X¹, X², L¹, L², L³, R¹, and R² are as defined for any of thepreviously defined groups of catalysts;

r and s are independently 0 or 1;

t is an integer in the range of 0 to 5;

k is an integer in the range of 0 to 1;

Y is any non-coordinating anion (e.g., a halide ion, BF₄ ⁻, etc.);

Z¹ and Z² are independently selected from —O—, —S—, —NR²—, —PR²—,—P(=O)R²—, —P(OR²)—, —P(=O)(OR²)—, —C(=O)—, —C(=O)O—, —OC(=O)—,—OC(=O)O—, —S(=O)—, —S(=O)₂—, -, and an optionally substituted and/oroptionally heteroatom containing C₁-C₂₀ hydrocarbylene linkage;

Z³ is any cationic moiety such as —P(R²)₃ ⁺ or —N(R²)₃ ⁺; and

any two or more of X¹, X², L¹, L², L³, Z¹, Z², Z³, R¹, and R² may betaken together to form a cyclic group, e.g., a multidentate ligand.

The Group 8 transition metal complexes having the structure of Formulae(VIII) to (XI) may be in a racemic isomeric form, a meso isomeric form,or a mixture of the racemic and meso isomeric forms.

Additionally, another group of metal carbene olefin metathesis catalyststhat may be used in the invention disclosed herein, is a Group 8transition metal complex having the structure of Formula (XII):

wherein: M is a Group 8 transition metal, particularly Ru or Os, or moreparticularly, Ru; L¹ is represented by the structures of Formula (II) orby the structures of Formula (III); X¹, X², and L² are as defined forthe first and second groups of catalysts defined above; and R^(G1),R^(G2), R^(G3), R^(G4), R^(G5), R^(G6) are each independently selectedfrom the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl,aryl, heteroalkyl, heteroatom containing alkenyl, heteroalkenyl,heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl,alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl,dialkylaminosulfonyl, alkyl sulfonyl, nitrile, nitro, alkylsulfinyl,trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde,nitrate, cyano, isocyanate, thioisocyanate, cyanato, thiocyanato,hydroxyl, ester, ether, thioether, amine, alkylamine, imine, amide,halogen-substituted amide, trifluoroamide, sulfide, disulfide,sulfonate, carbamate, silane, siloxane, phosphine, phosphate, borate,or-A-Fn, wherein “A” is a divalent hydrocarbon moiety selected fromalkylene and arylalkylene, wherein the alkyl portion of the alkylene andarylalkylene groups can be linear or branched, saturated or unsaturated,cyclic or acyclic, and substituted or unsubstituted, wherein the arylportion of the arylalkylene can be substituted or unsubstituted, andwherein hetero atoms and/or functional groups may be present in eitherthe aryl or the alkyl portions of the alkylene and arylalkylene groups,and Fn is a functional group, or any one or more of the R^(G1), R^(G2),R^(G3), R^(G4), R^(G5), and R^(G6) may be linked together to form acyclic group.

The Group 8 transition metal complex having the structure of Formula(XII) may be in a racemic isomeric form, a meso isomeric form, or amixture of the racemic and meso isomeric forms.

Additionally, one preferred embodiment of the Group 8 transition metalcomplex of Formula (XII) is a Group 8 transition metal complex ofFormula (XIII)

wherein: L¹ is represented by the structure of Formula (II) or by thestructure of Formula (III); M, X¹, X², and L² are as defined above forGroup 8 transition metal complex of Formula (XII); and R^(G7), R^(G8),R^(G9), R^(G10), R^(G11), R^(G12), R^(G13), R^(G14), R^(G15), andR^(G16) are as defined above for R^(G1), R^(G2), R^(G3), R^(G4), R^(G5),and R^(G6) for Group 8 transition metal complex of Formula (XII) or anyone or more of the R^(G7), R^(G8), R^(G9), R^(G10), R^(G11), R^(G12),R^(G13), R^(G14), R^(G15), and R^(G16) may be linked together to form acyclic group.

The Group 8 transition metal complex having the structure of Formula(XIII) may be in a racemic isomeric form, a meso isomeric form, or amixture of the racemic and meso isomeric forms.

Additionally, another preferred embodiment of the Group 8 transitionmetal complex of Formula (XII) is a Group 8 transition metal complex ofFormula (XIV):

wherein: L¹ is represented by Formula (II) or by Formula (III); M, X¹,X², and L² are as defined above for Group 8 transition metal complex ofFormula (XII).

The Group 8 transition metal complex having the structure of Formula(XIV) may be in a racemic isomeric form, a meso isomeric form, or amixture of the racemic and meso isomeric forms.

Additionally, another group of metal carbene olefin metathesis catalyststhat may be used in the invention disclosed herein, is a Group 8transition metal complex comprising a Schiff base ligand having thestructure of Formula (XV):

wherein:

M is a Group 8 transition metal, particularly Ru or Os, or moreparticularly, Ru;

L¹ is represented by the structure of Formula (II) or by the structureof Formula (III); X¹ is as defined for the first and second groups ofcatalysts defined above;

Z is selected from the group consisting of oxygen, sulfur, selenium,NR^(J11), PR^(J11), AsR^(J11), and SbR^(J11); and

R^(J1), R^(J2), R^(J3), R^(J4), R^(J5), R^(J6), R^(J7), R^(J8), R^(J9),R^(J10), and R^(J11) are each independently selected from the groupconsisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl,heteroalkyl, heteroatom containing alkenyl, heteroalkenyl, heteroaryl,alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino,alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl,alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl,perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano,isocyanate, thioisocyanate, cyanato, thiocyanato, hydroxyl, ester,ether, thioether, amine, alkylamine, imine, amide, halogen-substitutedamide, trifluoroamide, sulfide, disulfide, sulfonate, carbamate, silane,siloxane, phosphine, phosphate, borate, or-A-Fn, wherein “A” is adivalent hydrocarbon moiety selected from alkylene and arylalkylene,wherein the alkyl portion of the alkylene and arylalkylene groups can belinear or branched, saturated or unsaturated, cyclic or acyclic, andsubstituted or unsubstituted, wherein the aryl portion of thearylalkylene can be substituted or unsubstituted, and wherein heteroatoms and/or functional groups may be present in either the aryl or thealkyl portions of the alkylene and arylalkylene groups, and Fn is afunctional group, or any one or more of the R^(J1), R^(J2), R^(J3),R^(J4), R^(J5), R^(J6), R^(J7), R^(J8), R^(J9), R^(J10), and R^(j11) maybe linked together to form a cyclic group.

The Group 8 transition metal complex having the structure of Formula(XV) may be in a racemic isomeric form, a meso isomeric form, or amixture of the racemic and meso isomeric forms.

Additionally, another group of metal carbene olefin metathesis catalyststhat may be used in the invention disclosed herein, is a Group 8transition metal complex comprising a Schiff base ligand having thestructure of Formula (XVI):

wherein:

M is a Group 8 transition metal, particularly Ru or Os, or moreparticularly, Ru;

L¹ is represented by Formula (II) or by Formula (III); X¹, L¹, R¹, andR² are as defined for the first and second groups of catalysts definedabove;

Z is selected from the group consisting of oxygen, sulfur, selenium,NR^(K5), PR^(K5), AsR^(K5), and SbR^(K5);

m is 0, 1, or 2; and

R^(K1), R^(K2), R^(K3), R^(K4), and R^(K5) are each independentlyselected from the group consisting of hydrogen, halogen, alkyl, alkenyl,alkynyl, aryl, heteroalkyl, heteroatom containing alkenyl,heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl,carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl,dialkylaminosulfonyl, alkyl sulfonyl, nitrile, nitro, alkylsulfinyl,trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde,nitrate, cyano, isocyanate, thioisocyanate, cyanato, thiocyanato,hydroxyl, ester, ether, thioether, amine, alkylamine, imine, amide,halogen-substituted amide, trifluoroamide, sulfide, disulfide,sulfonate, carbamate, silane, siloxane, phosphine, phosphate, borate,or-A-Fn, wherein “A” is a divalent hydrocarbon moiety selected fromalkylene and arylalkylene, wherein the alkyl portion of the alkylene andarylalkylene groups can be linear or branched, saturated or unsaturated,cyclic or acyclic, and substituted or unsubstituted, wherein the arylportion of the arylalkylene can be substituted or unsubstituted, andwherein hetero atoms and/or functional groups may be present in eitherthe aryl or the alkyl portions of the alkylene and arylalkylene groups,and Fn is a functional group, or any one or more of the R^(K1), R^(K2),R^(K3), R^(K4), and R^(K5) may be linked together to form a cyclicgroup.

The Group 8 transition metal complex having the structure of Formula(XVI) may be in a racemic isomeric form, a meso isomeric form, or amixture of the racemic and meso isomeric forms.

In addition, catalysts of Formulae (XV) and (XVI) may be optionallycontacted with an activating compound, where at least partial cleavageof a bond between the Group 8 transition metal and at least one Schiffbase ligand occurs, wherein the activating compound is either a metal orsilicon compound, inorganic acid, or organic acid.

Examples of preferred metal carbene olefin metathesis catalysts have thestructure of Formula (I), wherein:

M is a Group 8 transition metal;

L¹ is represented by the structure of Formula (II) or by the structureof Formula (III);

L² and L³ are neutral electron donor ligands;

n is 0 or 1;

m is 0, 1, or 2;

k is 0 or 1;

X¹ and X² are anionic ligands;

R¹ and R² are independently selected from hydrogen, hydrocarbyl,substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substitutedheteroatom-containing hydrocarbyl, and functional groups, wherein anytwo or more of X¹, X², L¹, L², L³, and R² can be taken together to formone or more cyclic groups;

R^(V1), R^(V2), R^(V3), R^(V4), and R^(V5) are independently hydrogen,substituted branched C₁-C₆ alkyl, C₄-C₁₀ cycloalkyl, substituted C₄-C₁₀cycloalkyl, C₄-C₁₀ heteroatom-containing cycloalkyl, substituted C₄-C₁₀heteroatom-containing cycloalkyl, C₅-C₁₄ aryl, substituted C₅-C₁₄ aryl;and

R¹¹, R¹², R^(11a), and R^(12a) are independently hydrogen, C₁-C₁₂ alkyl,substituted C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy, substituted C₁-C₁₂ alkoxy,C₅-C₁₄ aryl, substituted C5-C14 aryl, or halide;

at least one of R^(V1), R^(V2), R^(V3), R^(V4), or R^(V5) is representedby a group such as:

“a” represents 0, 1, 2, 3, 4, or 5; and

R is substituted C₁-C₆ alkyl, C₁-C₆ alkyl, substituted C₃-C₁₀cycloalkyl, C₃-C₁₀ cycloalkyl, or halogen, wherein the catalyst may bein a racemic isomeric form, a meso isomeric form, or a mixture of theracemic and meso isomeric forms.

Examples of preferred metal carbene olefin metathesis catalysts have thestructure of Formula (VI), wherein:

M is Ru or Os;

L¹ is represented by the structure of Formula (II) or by the structureof Formula (III);

X¹ and X² are anionic ligands;

Y is a heteroatom selected from O or N;

R⁵, R⁶, R⁷, and R⁸ are independently selected from hydrogen,hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl,substituted heteroatom-containing hydrocarbyl, and functional groups;

n is 0, 1, or 2; and

Z is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl,heteroatom-containing hydrocarbyl, substituted heteroatom-containinghydrocarbyl, and functional groups; wherein any combination of Y, Z, R⁵,R⁶, R⁷, and R⁸ can be linked to form one or more cyclic groups;

R^(V1), R^(V2), R^(V3), R^(V4), and R^(V5) are independently hydrogen,substituted branched C₁-C₆ alkyl, C₄-C₁₀ cycloalkyl, substituted C₄-C₁₀cycloalkyl, C₄-C₁₀ heteroatom-containing cycloalkyl, substituted C₄-C₁₀heteroatom-containing cycloalkyl, C₅-C₁₄ aryl, substituted C₅-C₁₄ aryl;and

R¹¹, R¹², R^(11a), and R^(12a) are independently hydrogen, C₁-C₁₂ alkyl,substituted C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy, substituted C₁-C₁₂ alkoxy,C₅-C₁₄ aryl, substituted C₅-C₁₄ aryl, or halide; at least one of R^(V1),R^(V2), R^(V3), R^(V4), or R^(V5) is represented by a group such as:

“a” represents 0, 1, 2, 3, 4, or 5; and

R is substituted C₁-C₆ alkyl, C₁-C₆ alkyl, substituted C₃-C₁₀cycloalkyl, C₃-C₁₀ cycloalkyl or halogen, wherein the catalyst may be ina racemic isomeric form, a meso isomeric form, or a mixture of theracemic and meso isomeric forms.

Examples of preferred metal carbene olefin metathesis catalysts have thestructure of Formula (I), wherein:

M is Ru;

n is 0;

m is 0;

k is 1;

L¹ is represented by the structure of Formula (II) or by the structureof Formula (III);

L² is trisubstituted phosphines selected from the group consisting oftri-n-butylphosphine (Pn-Bu₃), tricyclopentylphosphine (PCp₃),tricyclohexylphosphine (PCy₃), triisopropylphosphine (P-i-Pr₃),triphenylphosphine (PPh₃), methyldiphenylphosphine (PMePh₂),dimethylphenylphosphine (PMe₂Ph), and diethylphenylphosphine (PEt₂Ph);or L¹ is an N-heterocyclic carbene selected from the group consisting of1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene,1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene,1,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and1,3-bis(2,6-di-isopropylphenyl)imidazol-2-ylidene and L² is atrisubstituted phosphine selected from the group consisting oftri-n-butylphosphine (Pn-Bu₃), tricyclopentylphosphine (PC₃),tricyclohexylphosphine (PCy₃), triisopropylphosphine (P-i-Pr₃),triphenylphosphine (PPh₃), methyldiphenylphosphine (PMePh₂),dimethylphenylphosphine (PMe₂Ph), and diethylphenylphosphine (PEt₂Ph);

X¹ and X² are chloride;

R¹ is hydrogen and R² is phenyl or —CH═C(CH₃)₂ or thienyl; or R¹ and R²are taken together to form phenylindenylidene;

R^(V1), R^(V2), R^(V3), R^(V4), and R^(V5) are independently hydrogen,substituted branched C₁-C₆ alkyl, C₄-C₁₀ cycloalkyl, substituted C₄-C₁₀cycloalkyl, C₄-C₁₀ heteroatom-containing cycloalkyl, substituted C₄-C₁₀heteroatom-containing cycloalkyl, C₅-C₁₄ aryl, substituted C₅-C₁₄ aryl;and

R¹¹, R¹², R^(11a), and R^(12a) are independently hydrogen, C₁-C₁₂ alkyl,substituted C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy, substituted C₁-C₁₂ alkoxy,C₅-C₁₄ aryl, substituted C₅-C₁₄ aryl, or halide; at least one of R^(V1),R^(V2), R^(V3), R^(V4), or R^(V5) is represented by a group such as:

“a” represents 0, 1, 2, 3, 4, or 5; and

R is substituted C₁-C₆ alkyl, C₁-C₆ alkyl, substituted C₃-C₁₀cycloalkyl, C₃-C₁₀ cycloalkyl, or halogen, wherein the catalyst may bein a racemic isomeric form, a meso isomeric form, or a mixture of theracemic and meso isomeric forms.

Examples of preferred metal carbene olefin metathesis catalysts have thestructure of Formula (VI), wherein:

M is Ru;

L¹ is represented by the structure of Formula (II) or by the structureof Formula (III);

X¹ and X² are chloride;

Y is oxygen;

R⁵, R⁶, R⁷, and R⁸ are each hydrogen;

n is 1;

Z is isopropyl;

R^(V1), R^(V2), R^(V3), R^(V4), and R^(V5) are independently hydrogen,substituted branched C₁-C₆ alkyl, C₄-C₁₀ cycloalkyl, substituted C₄-C₁₀cycloalkyl, C₄-C₁₀ heteroatom-containing cycloalkyl, substituted C₄-C₁₀heteroatom-containing cycloalkyl, C₅-C₁₄ aryl, substituted C₅-C₁₄ aryl;

R¹¹, R¹², R^(11a), R^(12a) are independently hydrogen, C₁-C₁₂ alkyl,substituted C₁-C ₁₂ alkyl, C₁-C₁₂ alkoxy, substituted C₁-C₁₂ alkoxy,C₅-C₁₄ aryl, substituted C₅-C₁₄ aryl, or halide; at least one of R^(V1),R^(V2), R^(V3), R⁴, or R^(V5) is represented by a group such as:

“a” represents 0, 1, 2, 3, 4, or 5; and

R is substituted C₁-C₆ alkyl, C₁-C₆ alkyl, substituted C₃-C₁₀cycloalkyl, C₃-C₁₀ cycloalkyl, or halogen, wherein the catalyst may bein a racemic isomeric form, a meso isomeric form, or a mixture of theracemic and meso isomeric forms.

Examples of preferred metal carbene olefin metathesis catalysts have thestructure of Formula (I), wherein:

M is Ru;

n is 0;

m is 0;

k is 1;

L¹ is represented by the structure of Formula (II) or by the structureof Formula (III);

L² is a trisubstituted phosphine independently selected from the groupconsisting of tri-n-butylphosphine (Pn-Bu₃), tricyclopentylphosphine(PCp₃), tricyclohexylphosphine (PCy₃), triisopropylphosphine (P-i-Pr₃),triphenylphosphine (PPh₃), methyldiphenylphosphine (PMePh₂),dimethylphenylphosphine (PMe₂Ph), and diethylphenylphosphine (PEt₂Ph);

X¹ and X² are chloride;

R¹ is hydrogen and R² is phenyl or —CH═C(CH₃)₂ or thienyl; or R¹ and R²are taken together to form phenylindenylidene;

R^(V1), R^(V2), R^(V3), R^(V4), and R^(V5) are independently hydrogen,substituted branched C₁-C₆ alkyl, C₄-C₁₀ cycloalkyl, substituted C₄-C₁₀cycloalkyl, C₄-C₁₀ heteroatom-containing cycloalkyl, substituted C₄-C₁₀heteroatom-containing cycloalkyl, C₅-C₁₄ aryl, substituted C₅-C₁₄ aryl;and

R¹¹, R¹², R^(11a), and R^(12a) are independently hydrogen, C₁-C₁₂ alkyl,substituted C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy, substituted C₁-C₁₂ alkoxy,C₅-C₁₄ aryl, substituted C₅-C₁₄ aryl, or halide; at least one of R^(V1),R^(V2), R^(V3), R^(V4), or R^(V5) is represented by a group such as:

“a” represents 0, 1, 2, 3, 4, or 5; and

R is substituted C₁-C₆ alkyl, C₁-C₆ alkyl, substituted C₃-C₁₀cycloalkyl, C₃-C₁₀ cycloalkyl, or halogen, wherein the catalyst may bein a racemic isomeric form, a meso isomeric form, or a mixture of theracemic and meso isomeric forms, wherein the catalyst may be in aracemic isomeric form, a meso isomeric form, or a mixture of the racemicand meso isomeric forms.

The catalysts of the invention may be utilized in olefin metathesisreactions according to techniques known in the art. The catalysts of theinvention are typically used as a solid, a solution, or as a suspension.When the catalysts of the invention are used as a suspension, thecatalysts of the invention are suspended in a dispersing carrier such asmineral oil, paraffin oil, soybean oil, tri-isopropylbenzene, or anyhydrophobic liquid which has a sufficiently high viscosity so as topermit effective dispersion of the catalyst(s), and which issufficiently inert and which has a sufficiently high boiling point sothat is does not act as a low-boiling impurity in the olefin metathesisreaction. It will be appreciated that the amount of catalyst that isused (i.e., the “catalyst loading”) in the reaction is dependent upon avariety of factors such as the identity of the reactants and thereaction conditions that are employed. It is therefore understood thatcatalyst loading may be optimally and independently chosen for eachreaction. In general, however, the catalyst will be present in an amountthat ranges from a low of about 0.1 ppm, 1 ppm, or 5 ppm, to a high ofabout 10 ppm, 15 ppm, 25 ppm, 50 ppm, 100 ppm, 200 ppm, 500 ppm, or 1000ppm relative to the amount of an olefinic substrate.

The catalyst will generally be present in an amount that ranges from alow of about 0.00001 mol %, 0.0001 mol %, or 0.0005 mol %, to a high ofabout 0.001 mol %, 0.0015 mol %, 0.0025 mol %, 0.005 mol %, 0.01 mol %,0.02 mol %, 0.05 mol %, or 0.1 mol % relative to the olefinic substrate.

When expressed as the molar ratio of monomer to catalyst, the catalyst(the “monomer to catalyst ratio”), loading will generally be present inan amount that ranges from a low of about 10,000,000:1, 1,000,000:1,500,000:1 or 200,00:1, to a high of about 100,000:1 60,000:1, 50,000:1,45,000;1, 40,000:1, 30,000:1, 20,000:1, 10,000:1, 5,000:1, or 1,000:1.

In one embodiment, the invention provides metal carbene olefinmetathesis catalysts of structures:

wherein the catalysts may be in a racemic isomeric form, a meso isomericform, or a mixture of the racemic and meso isomeric forms.

Cyclic Olefins

One or more cyclic olefins may be used with the present inventiondisclosed herein. In general, any cyclic olefin suitable for themetathesis reactions disclosed herein may be used. Such cyclic olefinsmay be optionally substituted, optionally heteroatom-containing,mono-unsaturated, di-unsaturated, or poly-unsaturated C₅ to C₂₄hydrocarbons that may be mono-, di-, or poly-cyclic. The cyclic olefinmay generally be any strained or unstrained cyclic olefin, provided thecyclic olefin is able to participate in a metathesis reaction (e.g.,ROMP, ROCM, etc.). While certain unstrained cyclic olefins such ascyclohexene are generally understood to not undergo ROMP reactions bythemselves, under appropriate circumstances, such unstrained cyclicolefins may nonetheless be ROMP active. For example, when present as aco-monomer in a ROMP composition, unstrained cyclic olefins may be ROMPactive. Accordingly, as used herein and as would be appreciated by theskilled artisan, the term “unstrained cyclic olefin” is intended torefer to those unstrained cyclic olefins that may undergo a ROMPreaction under any conditions, or in any ROMP composition, provided theunstrained cyclic olefin is ROMP active.

In general, the cyclic olefin may be represented by the structure ofFormula (A)

wherein J, R^(A1), and R^(A2) are as follows: R^(A1) and R^(A2) isselected independently from the group consisting of hydrogen,hydrocarbyl (e.g., C₁-C₂₀ alkyl, C₅-C₂₀ aryl, C₅-C₃₀ aralkyl, or C₅-C₃₀alkaryl), substituted hydrocarbyl (e.g., substituted C₁-C₂₀ alkyl,C₅-C₂₀ aryl, C₅-C₃₀ aralkyl, or C₅-C₃₀ alkaryl), heteroatom-containinghydrocarbyl (e.g., C₁-C₂₀ heteroalkyl, C₅-C₂₀ heteroaryl,heteroatom-containing C₅-C₃₀ aralkyl, or heteroatom-containing C₅-C₃₀alkaryl), and substituted heteroatom-containing hydrocarbyl (e.g.,substituted C₁-C₂₀ heteroalkyl, C₅-C₂₀ heteroaryl, heteroatom-containingC₅-C₃₀ aralkyl, or heteroatom-containing C₅-C₃₀ alkaryl) and, ifsubstituted hydrocarbyl or substituted heteroatom-containinghydrocarbyl, wherein the substituents may be functional groups (“Fn”)such as phosphonato, phosphoryl, phosphanyl, phosphino, sulfonato,C₁-C₂₀ alkyl sulfanyl, C₅-C₂₀ aryl sulfanyl, C₁-C₂₀ alkyl sulfonyl,C₅-C₂₀ aryl sulfonyl, C₁-C₂₀ alkylsulfinyl, C₅-C₂₀ arylsulfinyl,sulfonamido, amino, amido, imino, nitro, nitroso, hydroxyl, C₁-C₂₀alkoxy, C₅-C₂₀ aryloxy, C₂-C₂₀ alkoxycarbonyl, C₅-C₂₀ aryloxycarbonyl,carboxyl, carboxylato, mercapto, formyl, C₁-C₂₀ thioester, cyano,cyanato, thiocyanato, isocyanate, thioisocyanate, carbamoyl, epoxy,styrenyl, silyl, silyloxy, silanyl, siloxazanyl, boronato, boryl, orhalogen, or a metal-containing or metalloid-containing group (whereinthe metal may be, for example, Sn or Ge). R^(A1) and R^(A2) may itselfbe one of the aforementioned groups, such that the Fn moiety is directlybound to the olefinic carbon atom indicated in the structure. In thelatter case, however, the functional group will generally not bedirectly bound to the olefinic carbon through a heteroatom containingone or more lone pairs of electrons, e.g., an oxygen, sulfur, nitrogen,or phosphorus atom, or through an electron-rich metal or metalloid suchas Ge, Sn, As, Sb, Se, Te, etc. With such functional groups, there willnormally be an intervening linkage Z*, such that R^(A1) and/or R^(A2)then has the structure —(Z*)_(n)-Fn wherein n is 1, Fn is the functionalgroup, and Z* is a hydrocarbylene linking group such as an alkylene,substituted alkylene, heteroalkylene, substituted heteroalkene, arylene,substituted arylene, heteroarylene, or substituted heteroarylenelinkage. J is a saturated or unsaturated hydrocarbylene, substitutedhydrocarbylene, heteroatom-containing hydrocarbylene, or substitutedheteroatom-containing hydrocarbylene linkage, wherein when J issubstituted hydrocarbylene or substituted heteroatom-containinghydrocarbylene, the substituents may include one or more —(Z*)_(n)-Fngroups, wherein n is 0 or 1, and Fn and Z* are as defined previously.Additionally, two or more substituents attached to ring carbon (orother) atoms within J may be linked to form a bicyclic or polycyclicolefin. J will generally contain in the range of approximately 5 to 14ring atoms, typically 5 to 8 ring atoms, for a monocyclic olefin, and,for bicyclic and polycyclic olefins, each ring will generally contain 4to 8, typically 5 to 7, ring atoms.

Mono-unsaturated cyclic olefins encompassed by Formula (A) may berepresented by the Formula (B):

wherein b is an integer generally although not necessarily in the rangeof 1 to 10, typically 1 to 5, R^(A1) and R^(A2) are as defined above forFormula (A), and R^(B1), R^(B2), R^(B3), R^(B4), R^(B5), and R^(B6) areindependently selected from the group consisting of hydrogen,hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl,substituted heteroatom-containing hydrocarbyl and —(Z*)_(n)-Fn where n,Z* and Fn are as defined previously, and wherein if any of the R^(B1)through R^(B6) moieties is substituted hydrocarbyl or substitutedheteroatom-containing hydrocarbyl, the substituents may include one ormore —(Z*)_(n)-Fn groups. Accordingly, R^(B1), R^(B2), R^(B3), R^(B4),R^(B5), and R^(B6) may be, for example, hydrogen, hydroxyl, C₁-C₂₀alkyl, C₅-C₂₀ aryl, C₁-C₂₀ alkoxy, C₅-C₂₀ aryloxy, C₂-C₂₀alkoxycarbonyl, C₂-C₂₄ alkylcarbonyloxy, C₅-C₂₀ aryloxycarbonyl, amino,amido, nitro, etc.

Furthermore, any of the R^(B1), R^(B2), R^(B3), R^(B4), R^(B5), andR^(B6) moieties can be linked to any of the other R^(B1), R^(B2),R^(B3), R^(B4), R^(B5), and R^(B6) moieties to provide a substituted orunsubstituted alicyclic group containing 4 to 30 ring carbon atoms or asubstituted or unsubstituted aryl group containing 6 to 18 ring carbonatoms or combinations thereof and the linkage may include heteroatoms orfunctional groups, e.g., the linkage may include without limitation anether, ester, thioether, amino, alkylamino, imino, or anhydride moiety.The alicyclic group can be monocyclic, bicyclic, or polycyclic. Whenunsaturated the cyclic group can contain monounsaturation ormultiunsaturation, with monounsaturated cyclic groups being preferred.When substituted, the rings contain monosubstitution ormultisubstitution wherein the substituents are independently selectedfrom hydrogen, hydrocarbyl, substituted hydrocarbyl,heteroatom-containing hydrocarbyl, substituted heteroatom-containinghydrocarbyl, —(Z*)_(n)-Fn where n is 0 or 1, Z* and Fn are as definedpreviously, and functional groups (Fn) provided above.

Examples of monounsaturated, monocyclic olefins encompassed by Formula(B) include, without limitation, cyclopentene, cyclohexene,cycloheptene, cyclooctene, cyclononene, cyclodecene, cycloundecene,cyclododecene, tricyclodecene, tetracyclodecene, octacyclodecene, andcycloeicosene, and substituted versions thereof such as1-methylcyclopentene, 1-ethylcyclopentene, 1-isopropylcyclohexene,1-chloropentene, 1-fluorocyclopentene, 4-methylcyclopentene,4-methoxy-cyclopentene, 4-ethoxy-cyclopentene, cyclopent-3-ene-thiol,cyclopent-3-ene, 4-methylsulfanyl-cyclopentene, 3-methylcyclohexene,1-methylcyclooctene, 1,5-dimethylcyclooctene, etc.

Monocyclic diene reactants encompassed by Formula (A) may be generallyrepresented by the Formula (C):

wherein c and d are independently integers in the range of 1 to about 8,typically 2 to 4, preferably 2 (such that the reactant is acyclooctadiene), R^(A1) and R^(A2) are as defined above for Formula (A)and R^(C1), R^(C2), R^(C3), R^(C4), R^(C5), and R^(C6) are defined asfor R^(B1) through R^(B6). In this case, it is preferred that R^(C3) andR^(C4) be non-hydrogen substituents, in which case the second olefinicmoiety is tetrasubstituted. Examples of monocyclic diene reactantsinclude, without limitation, 1,3-cyclopentadiene, 1,3-cyclohexadiene,1,4-cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, 1,3-cycloheptadiene,cyclohexadiene, 1,5-cyclooctadiene, 1,3-cyclooctadiene, and substitutedanalogs thereof. Triene reactants are analogous to the diene Formula(C), and will generally contain at least one methylene linkage betweenany two olefinic segments.

Bicyclic and polycyclic olefins encompassed by Formula (A) may begenerally represented by the Formula (D):

wherein R^(A1) and R^(A2) are as defined above for Formula (A), R^(D1),R^(D2), R^(D3), and R^(D4) are as defined for R^(B1) through R^(B6), eis an integer in the range of 1 to 8 (typically 2 to 4), f is generally1 or 2; T is lower alkylene or alkenylene (generally substituted orunsubstituted methyl or ethyl), CHR^(G1), C(R^(G1))₂, O, S, N—R^(G1),P—R^(G1), O═P—R^(G1), Si(R^(G1))₂, B—R^(G1), or As—R^(G1) where R^(G1)is alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, alkaryl, aralkyl, oralkoxy. Furthermore, any of the R^(D1), R^(D2), R^(D3), and R^(D4)moieties can be linked to any of the other R^(D1), R^(D2), R^(D3), andR^(D4) moieties to provide a substituted or unsubstituted alicyclicgroup containing 4 to 30 ring carbon atoms or a substituted orunsubstituted aryl group containing 6 to 18 ring carbon atoms orcombinations thereof and the linkage may include heteroatoms orfunctional groups, e.g., the linkage may include without limitation anether, ester, thioether, amino, alkylamino, imino, or anhydride moiety.The cyclic group can be monocyclic, bicyclic, or polycyclic. Whenunsaturated the cyclic group can contain monounsaturation ormultiunsaturation, with monounsaturated cyclic groups being preferred.When substituted, the rings contain monosubstitution or multisubstitution wherein the substituents are independently selected fromhydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containinghydrocarbyl, substituted heteroatom-containing hydrocarbyl, —(Z*)_(n)-Fnwhere n is 0 or 1, Z* and Fn are as defined previously, and functionalgroups (Fn) provided above.

Cyclic olefins encompassed by Formula (D) are in the norbornene family.As used herein, norbornene means any compound that includes at least onenorbornene or substituted norbornene moiety, including withoutlimitation norbornene, substituted norbornene(s), norbornadiene,substituted norbornadiene(s), polycyclic norbornenes, and substitutedpolycyclic norbornene(s). Norbornenes within this group may be generallyrepresented by the Formula (E):

wherein R^(A1) and R^(A2) are as defined above for Formula (A), T is asdefined above for Formula (D) R^(E1), R^(E2), R^(E3), R^(E4), R^(E5),R^(E6), R^(E7), and R^(E8) are as defined for R^(B1) through R^(B6), and“a” represents a single bond or a double bond, f is generally 1 or 2,“g” is an integer from 0 to 5, and when “a” is a double bond one ofR^(E5), R^(E6) and one of R^(E7), R^(E8) is not present.

Furthermore, any of the R^(E5), R^(E6), R^(E7), and R^(E8) moieties canbe linked to any of the other R^(E5), R^(E6), R^(E7), and R^(E8)moieties to provide a substituted or unsubstituted alicyclic groupcontaining 4 to 30 ring carbon atoms or a substituted or unsubstitutedaryl group containing 6 to 18 ring carbon atoms or combinations thereofand the linkage may include heteroatoms or functional groups, e.g., thelinkage may include without limitation an ether, ester, thioether,amino, alkylamino, imino, or anhydride moiety. The cyclic group can bemonocyclic, bicyclic, or polycyclic. When unsaturated the cyclic groupcan contain monounsaturation or multiunsaturation, with monounsaturatedcyclic groups being preferred. When substituted, the rings containmonosubstitution or multisubstitution wherein the substituents areindependently selected from hydrogen, hydrocarbyl, substitutedhydrocarbyl, heteroatom-containing hydrocarbyl, substitutedheteroatom-containing hydrocarbyl, —(Z*)_(n)-Fn where n is 0 or 1, Z*and Fn are as defined previously, and functional groups (Fn) providedabove.

More preferred cyclic olefins possessing at least one norbornene moietyhave the Formula (F):

wherein R^(F1), R^(F2), R^(F3), and R^(F4), are as defined for R^(B1)through R^(B6), and “a” represents a single bond or a double bond, “g”is an integer from 0 to 5, and when “a” is a double bond one of R^(F1),R^(F2) and one of R^(F3), R^(F4) is not present.

Furthermore, any of the R^(F1), R^(F2), R^(F3), and R^(F4) moieties canbe linked to any of the other R^(F1), R^(F2), R^(F3), and R^(F4)moieties to provide a substituted or unsubstituted alicyclic groupcontaining 4 to 30 ring carbon atoms or a substituted or unsubstitutedaryl group containing 6 to 18 ring carbon atoms or combinations thereofand the linkage may include heteroatoms or functional groups, e.g., thelinkage may include without limitation an ether, ester, thioether,amino, alkylamino, imino, or anhydride moiety. The alicyclic group canbe monocyclic, bicyclic, or polycyclic. When unsaturated the cyclicgroup can contain monounsaturation or multiunsaturation, withmonounsaturated cyclic groups being preferred. When substituted, therings contain monosubstitution or multisubstitution wherein thesubstituents are independently selected from hydrogen, hydrocarbyl,substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substitutedheteroatom-containing hydrocarbyl, —(Z*)_(n)-Fn where n is 0 or 1, Z*and Fn are as defined previously, and functional groups (Fn) providedabove.

Examples of bicyclic and polycyclic olefins thus include, withoutlimitation, dicyclopentadiene (DCPD); trimer and other higher orderoligomers of cyclopentadiene including without limitationtricyclopentadiene (cyclopentadiene trimer), cyclopentadiene tetramer(tetracyclopentadiene), and cyclopentadiene pentamer(pentacyclopentadiene); ethylidenenorbornene; dicyclohexadiene;norbornene; 5-methyl-2-norbornene; 5-ethyl-2-norbornene;5-isobutyl-2-norbornene; 5,6-dimethyl-2-norbornene; 5-phenylnorbornene;5-benzylnorbornene; 5-acetylnorbornene; 5-methoxycarbonylnorbornene;5-ethyoxycarbonyl-1-norbornene; 5-methyl-5-methoxy-carbonylnorbornene;5-cyanonorbornene; 5,5,6-trimethyl-2-norbornene;cyclo-hexenylnorbornene; endo, exo-5,6-dimethoxynorbornene; endo,endo-5,6-dimethoxynorbornene; endo, exo-5,6-dimethoxycarbonylnorbornene;endo, endo-5,6-dimethoxycarbonylnorbornene; 2,3-dimethoxynorbornene;norbornadiene; tricycloundecene; tetracyclododecene;8-methyltetracyclododecene; 8-ethyltetracyclododecene;8-methoxycarbonyltetracyclododecene; 8-methyl-8-tetracyclododecene;8-cyanotetracyclododecene; pentacyclopentadecene; pentacyclohexadecene;and the like, and their structural isomers, stereoisomers, and mixturesthereof. Additional examples of bicyclic and polycyclic olefins include,without limitation, C₂-C₁₂ hydrocarbyl substituted norbornenes such as5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene,5-decyl-2-norbornene, 5-dodecyl-2-norbornene, 5-vinyl-2-norbornene,5-ethylidene-2-norbornene, 5-isopropenyl-2-norbornene,5-propenyl-2-norbornene, and 5-butenyl-2-norbornene, and the like. It iswell understood by one of skill in the art that bicyclic and polycyclicolefins as disclosed herein may consist of a variety of structuralisomers and/or stereoisomers, any and all of which are suitable for usein the present invention. Any reference herein to such bicyclic andpolycyclic olefins unless specifically stated includes mixtures of anyand all such structural isomers and/or stereoisosmers.

Preferred cyclic olefins include C₅ to C₂₄ unsaturated hydrocarbons.Also preferred are C₅ to C₂₄ cyclic hydrocarbons that contain one ormore (typically 2 to 12) heteroatoms such as O, N, S, or P. For example,crown ether cyclic olefins may include numerous O heteroatoms throughoutthe cycle, and these are within the scope of the invention. In addition,preferred cyclic olefins are C₅ to C₂₄ hydrocarbons that contain one ormore (typically 2 or 3) olefins. For example, the cyclic olefin may bemono-, di-, or tri-unsaturated. Examples of cyclic olefins includewithout limitation cyclooctene, cyclododecene, and(c,t,t)-1,5,9-cyclododecatriene.

The cyclic olefins may also comprise multiple (typically 2 or 3) rings.For example, the cyclic olefin may be mono-, di-, or tri-cyclic. Whenthe cyclic olefin comprises more than one ring, the rings may or may notbe fused. Preferred examples of cyclic olefins that comprise multiplerings include norbornene, dicyclopentadiene, tricyclopentadiene, and5-ethylidene-2-norbornene.

The cyclic olefin may also be substituted, for example, a C₅ to C₂₄cyclic hydrocarbon wherein one or more (typically 2, 3, 4, or 5) of thehydrogens are replaced with non-hydrogen substituents. Suitablenon-hydrogen substituents may be chosen from the substituents describedhereinabove. For example, functionalized cyclic olefins, i.e., C₅ to C₂₄cyclic hydrocarbons wherein one or more (typically 2, 3, 4, or 5) of thehydrogens are replaced with functional groups, are within the scope ofthe invention. Suitable functional groups may be chosen from thefunctional groups described hereinabove. For example, a cyclic olefinfunctionalized with an alcohol group may be used to prepare a telechelicpolymer comprising pendent alcohol groups. Functional groups on thecyclic olefin may be protected in cases where the functional groupinterferes with the metathesis catalyst, and any of the protectinggroups commonly used in the art may be employed. Acceptable protectinggroups may be found, for example, in Greene et al., Protective Groups inOrganic Synthesis, 3rd Ed. (New York: Wiley, 1999). Examples offunctionalized cyclic olefins include without limitation2-hydroxymethyl-5-norbornene,2-[(2-hydroxyethyl)carboxylate]-5-norbornene, cydecanol,5-n-hexyl-2-norbornene, 5-n-butyl-2-norbornene.

Cyclic olefins incorporating any combination of the abovementionedfeatures (i.e., heteroatoms, substituents, multiple olefins, multiplerings) are suitable for the methods disclosed herein. Additionally,cyclic olefins incorporating any combination of the abovementionedfeatures (i.e., heteroatoms, substituents, multiple olefins, multiplerings) are suitable for the invention disclosed herein.

The cyclic olefins useful in the methods disclosed herein may bestrained or unstrained. It will be appreciated that the amount of ringstrain varies for each cyclic olefin compound, and depends upon a numberof factors including the size of the ring, the presence and identity ofsubstituents, and the presence of multiple rings. Ring strain is onefactor in determining the reactivity of a molecule towards ring openingolefin metathesis reactions. Highly strained cyclic olefins, such ascertain bicyclic compounds, readily undergo ring opening reactions witholefin metathesis catalysts. Less strained cyclic olefins, such ascertain unsubstituted hydrocarbon monocyclic olefins, are generally lessreactive. In some cases, ring opening reactions of relatively unstrained(and therefore relatively unreactive) cyclic olefins may become possiblewhen performed in the presence of the olefinic compounds disclosedherein. Additionally, cyclic olefins useful in the invention disclosedherein may be strained or unstrained.

A plurality of cyclic olefins may be used to prepare metathesis polymersfrom the olefinic compound. For example, two cyclic olefins selectedfrom the cyclic olefins described hereinabove may be employed in orderto form metathesis products that incorporate both cyclic olefins. Wheretwo or more cyclic olefins are used, one example of a second cyclicolefin is a cyclic alkenol, i.e., a C₅-C₂₄ cyclic hydrocarbon wherein atleast one of the hydrogen substituents is replaced with an alcohol orprotected alcohol moiety to yield a functionalized cyclic olefin.

The use of a plurality of cyclic olefins, and in particular when atleast one of the cyclic olefins is functionalized, allows for furthercontrol over the positioning of functional groups within the products.For example, the density of cross-linking points can be controlled inpolymers and macromonomers prepared using the methods disclosed herein.Control over the quantity and density of substituents and functionalgroups also allows for control over the physical properties (e.g.,melting point, tensile strength, glass transition temperature, etc.) ofthe products. Control over these and other properties is possible forreactions using only a single cyclic olefin, but it will be appreciatedthat the use of a plurality of cyclic olefins further enhances the rangeof possible metathesis products and polymers formed.

Examples of cyclic olefins include dicyclopentadiene;tricyclopentadiene; dicyclohexadiene; norbornene; 5-methyl-2-norbornene;5-ethyl-2-norbornene; 5-isobutyl-2-norbornene;5,6-dimethyl-2-norbornene; 5-phenylnorbornene; 5-benzylnorbornene;5-acetylnorbornene; 5-methoxycarbonylnorbornene;5-ethoxycarbonyl-1-norbornene; 5-methyl-5-methoxy-carbonylnorbornene;5-cyanonorbornene ; 5,5,6-trimethyl-2-norbornene ;cyclo-hexenylnorbornene; exo-5,6-dimethoxynorbornene; endo,endo-5,6-dimethoxynorbornene; endo, exo-5-6-dimethoxycarbonylnorbornene;endo, endo-5,6-dimethoxycarbonylnorbornene; 2,3-dimethoxynorbornene;norbornadiene; tricycloundecene; tetracyclododecene;8-methyltetracyclododecene; 8-ethyl-tetracyclododecene;8-methoxycarbonyltetracyclododecene; 8-methyl-8-tetracyclo-dodecene;8-cyanotetracyclododecene; pentacyclopentadecene; pentacyclohexadecene;higher order oligomers of cyclopentadiene such as cyclopentadienetetramer, cyclopentadiene pentamer, and the like; and C₂-C₁₂ hydrocarbylsubstituted norbornenes such as 5-butyl-2-norbornene;5-hexyl-2-norbornene; 5-octyl-2-norbornene; 5-decyl-2-norbornene;5-dodecyl-2-norbornene; 5-vinyl-2-norbornene; 5-ethylidene-2-norbornene;5-isopropenyl-2-norbornene; 5-propenyl-2-norbornene; and5-butenyl-2-norbornene, and the like. Examples of cyclic olefins includedicyclopentadiene, tricyclopentadiene, and higher order oligomers ofcyclopentadiene, such as cyclopentadiene tetramer, cyclopentadienepentamer, and the like, tetracyclododecene, norbornene, and C₂-C₁₂hydrocarbyl substituted norbornenes, such as 5-butyl-2-norbornene,5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-decyl-2-norbornene,5-dodecyl-2-norbornene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene,5-isopropenyl-2-norbornene, 5-propenyl-2-norbornene,5-butenyl-2-norbornene, and the like. Examples of cyclic olefins includedicyclopentadiene, tricyclopentadiene, and higher order oligomers ofcyclopentadiene, such as cyclopentadiene tetramer, cyclopentadienepentamer, and the like, tetracyclododecene, norbornene, and C₂-C₁₂hydrocarbyl substituted norbornenes, such as 5-butyl-2-norbornene,5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-decyl-2-norbornene,5-dodecyl-2-norbornene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene,5-isopropenyl-2-norbornene, 5-propenyl-2-norbornene,5-butenyl-2-norbornene, and the like. Examples of cyclic olefins includedicyclopentadiene, tricyclopentadiene, and higher order oligomers ofcyclopentadiene, such as cyclopentadiene tetramer, cyclopentadienepentamer, and the like, including structural isomers and/orstereoisomers, any and all of which are suitable for use in the presentinvention. Examples of cyclic olefins include dicyclopentadiene,tricyclopentadiene, and tetracyclopentadiene, including structuralisomers and/or stereoisomers, any and all of which are suitable for usein the present invention. Examples of cyclic olefins includedicyclopentadiene and tricyclopentadiene, including structural isomersand/or stereoisomers, any and all of which are suitable for use in thepresent invention.

Acyclic olefins suitable for use in the invention, include but are notlimited to non-substituted or substituted internal olefins,non-substituted or substituted terminal olefins, or non-substituted orsubstituted terminal dienes, where the substituents are selected fromhydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl,substituted heteroatom-containing hydrocarbyl, and functional groups.Acyclic olefins for use in the invention may contain monounsaturation ormultiunsaturation.

Olefin Reactant Comprising a Reactant Terminal Olefin

In one example an olefin reactant comprising a reactant terminal olefinmay be represented by the structure of Formula (G):

wherein D¹ and D² are independently selected from nil, CH₂, O, or S; andE¹ and E² are independently selected from hydrogen, hydrocarbyl (e.g.,C₁-C₂₀ alkyl, C₅-C₂₀ aryl, C₅-C₃₀ aralkyl, or C₅-C₃₀ alkaryl),substituted hydrocarbyl (e.g., substituted C₁-C₂₀ alkyl, C₅-C₂₀ aryl,C₅-C₃₀ aralkyl, or C₅-C₃₀ alkaryl), heteroatom-containing hydrocarbyl(e.g., C₁-C₂₀ heteroalkyl, C₅-C₂₀ heteroaryl, heteroatom-containingC₅-C₃₀ aralkyl, or heteroatom-containing C₅-C₃₀ alkaryl), andsubstituted heteroatom-containing hydrocarbyl (e.g., substituted C₁-C₂₀heteroalkyl, C₅-C₂₀ heteroaryl, heteroatom-containing C₅-C₃₀ aralkyl, orheteroatom-containing C₅-C₃₀ alkaryl) and, if substituted hydrocarbyl orsubstituted heteroatom-containing hydrocarbyl, wherein the substituentsmay be functional groups (“Fn”) such as halo, hydroxyl, sulfhydryl,C₁-C₂₄ alkoxy, C₅-C₂₄ aryloxy, C₆-C₂₄ aralkyloxy, C₆-C₂₄ alkaryloxy,acyl (including C₂-C₂₄ alkylcarbonyl (—CO-alkyl) and C₆-C₂₄ arylcarbonyl(—CO-aryl)), acyloxy (—O-acyl, including C₂-C₂₄ alkylcarbonyloxy(—O—CO-alkyl) and C₆-C₂₄ arylcarbonyloxy (—O—CO-aryl)), C₂-C₂₄alkoxycarbonyl (—(CO)—O-alkyl), C₆-C₂₄ aryloxycarbonyl (—(CO)—O-aryl),halocarbonyl (—CO)—X where X is halo), C₂-C₂₄ alkylcarbonato(—O—(CO)—O-alkyl), C₆-C₂₄ arylcarbonato (—O—(CO)—O-aryl), carboxy(—COOH), carboxylato (—COO³¹), carbamoyl (—(CO)—NH₂), mono-(C₁-C₂₄alkyl)-substituted carbamoyl (—(CO)—NH(C₁-C₂₄ alkyl)), di-(C₁-C₂₄alkyl)-substituted carbamoyl (—(CO)—N(C₁-C₂₄ alkyl)₂), mono-(C₁-C₂₄haloalkyl)-substituted carbamoyl (—(CO)—NH(C₁-C₂₄ haloalkyl)),di-(C₁-C₂₄ haloalkyl)-substituted carbamoyl (—(CO)—N(C₁-C₂₄haloalkyl)₂), mono-(C₅-C₂₄ aryl)-substituted carbamoyl (—(CO)—NH-aryl),di-(C₅-C₂₄ aryl)-substituted carbamoyl (—(CO)—N(C₅-C₂₄ aryl)₂),di-N—(C₁-C₂₄ alkyl), N—(C₅-C₂₄ aryl)-substituted carbamoyl(—(CO)—N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl), thiocarbamoyl (—(CS)—NH₂),mono-(C₁-C₂₄ alkyl)-substituted thiocarbamoyl (—(CS)—NH(C₁-C₂₄ alkyl)),di-(C₁-C₂₄ alkyl)-substituted thiocarbamoyl (—(CS)—N(C₁-C₂₄ alkyl)₂),mono-(C₅-C₂₄ aryl)-substituted thiocarbamoyl (—(CS)—NH-aryl), di-(C₅-C₂₄aryl)-substituted thiocarbamoyl (—(CS)—N(C₅-C₂₄ aryl)₂), di-N—(C₁-C₂₄alkyl), N—(C₅-C₂₄ aryl)-substituted thiocarbamoyl (—(CS)—N(C₁-C₂₄alkyl)(C₅-C₂₄ aryl), carbamido (—NH—(CO)—NH₂), cyano (—C≡N), cyanato(—O—C≡N), thiocyanato (—S—C≡N), isocyanate (—N═C═O), thioisocyanate(—N═C═S), formyl (—(CO)—H), thioformyl (—(CS)—H), amino (—NH₂),mono-(C₁-C₂₄ alkyl)-substituted amino (—NH(C₁-C₂₄ alkyl), di—(C₁-C₂₄alkyl)-substituted amino (—N(C₁-C₂₄ alkyl)₂), mono-(C₅-C₂₄aryl)-substituted amino (—NH(C₅-C₂₄ aryl), di-(C₅-C₂₄ aryl)-substitutedamino (—N(C₅-C₂₄ aryl)₂), C₂-C₂₄ alkylamido (—NH—(CO)-alkyl), C₆-C₂₄arylamido (—NH—(CO)-aryl), imino (—CR═NH where R includes withoutlimitation hydrogen, C₁-C₂₄ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄aralkyl, etc.), C₂-C₂₀ alkylimino (—CR═N(alkyl), where R includeswithout limitation hydrogen, C₁-C₂₄ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl,C₆-C₂₄ aralkyl, etc.), arylimino (—CR═N(aryl), where R includes withoutlimitation hydrogen, C₁-C₂₀ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆ ⁻C₂₄aralkyl, etc.), nitro (—NO₂), nitroso (—NO), sulfo (—SO₂—OH), sulfonato(—S₀₂—O⁻), C₁-C₂₄ alkyl sulfanyl (—S-alkyl; also termed “alkylthio”),C₅-C₂₄ aryl sulfanyl (—S-aryl; also termed “arylthio”), C₁-C₂₄alkylsulfinyl (—(SO)-alkyl), C₅-C₂₄ arylsulfinyl (—(SO)-aryl), C₁-C₂₄alkyl sulfonyl (—SO₂-alkyl), C₁-C₂₄ monoalkylaminosulfonyl (—SO₂—N(H)alkyl), C₁-C₂₄ dialkylaminosulfonyl (—SO₂—N(alkyl)₂), C₅-C₂₄arylsulfonyl (—SO₂-aryl), boryl (—BH₂), borono (—B(OH)₂), boronato(—B(OR)₂ where R is alkyl or aryl), phosphono (—P(O)(OH)₂), phosphonato(—P(O)(O⁻)₂), phosphinato (—P(O)(O⁻)), phospho (—PO₂), and phosphino(—PH₂); and the hydrocarbyl moieties C₁-C₂₄ alkyl (preferably C₁-C₁₂alkyl, more preferably C₁-C₆ alkyl), C₅-C₂₄ aryl (preferably C₅-C₁₄aryl), C₆-C₂₄ alkaryl (preferably C₆-C₁₆ alkaryl), and C₆-C₂₄ aralkyl(preferably C₆-C₁₆ aralkyl).

One or more olefin reactants comprising a reactant terminal olefin maybe used with the invention described herein, wherein the one or moreolefin reactants comprising a reactant terminal olefin may be the sameor different.

Olefin Reactant Comprising a Reactant Internal Olefin

One or more olefin reactants comprising a reactant internal olefin maybe used with the invention described herein, wherein the one or moreolefin reactants comprising a reactant internal olefin may be the sameor different.

In the one or more olefin reactants comprising a reactant internalolefin, the reactant internal olefin may be in the (Z)- or(E)-configuration. In one embodiment, in the one or more olefinreactants comprising a reactant internal olefin, the reactant internalolefin is in the (Z)-configuration. In one embodiment, in the one ormore olefin reactants comprising a reactant internal olefin, thereactant internal olefin is in the (E)-configuration.

In one example an olefin reactant comprising a reactant internal olefinmay be represented by the structure of Formula (H):

wherein D³, D⁴, D⁵, and D⁶ are independently selected from nil, CH₂, O,or S; and E³, E⁴, E⁵, and E⁶ are independently selected from hydrogen,hydrocarbyl (e.g., C₁-C₂₀ alkyl, C₅-C₂₀ aryl, C₅-C₃₀ aralkyl, or C₅-C₃₀alkaryl), substituted hydrocarbyl (e.g., substituted C₁-C₂₀ alkyl,C₅-C₂₀ aryl, C₅-C₃₀ aralkyl, or C₅-C₃₀ alkaryl), heteroatom-containinghydrocarbyl (e.g., C₁-C₂₀ heteroalkyl, C₅-C₂₀ heteroaryl,heteroatom-containing C₅-C₃₀ aralkyl, or heteroatom-containing C₅-C₃₀alkaryl), and substituted heteroatom-containing hydrocarbyl (e.g.,substituted C₁-C₂₀ heteroalkyl, C₅-C₂₀ heteroaryl, heteroatom-containingC₅-C₃₀ aralkyl, or heteroatom-containing C₅-C₃₀ alkaryl) and, ifsubstituted hydrocarbyl or substituted heteroatom-containinghydrocarbyl, wherein the substituents may be functional groups (“Fn”)such as halo, hydroxyl, sulfhydryl, C₁-C₂₄ alkoxy, C₅-C₂₄ aryloxy,C₆-C₂₄ aralkyloxy, C₆-C₂₄ alkaryloxy, acyl (including C₂-C₂₄alkylcarbonyl (—CO-alkyl) and C₆-C₂₄ arylcarbonyl (—CO-aryl)), acyloxy(—O-acyl, including C₂-C₂₄ alkylcarbonyloxy (—O—CO-alkyl) and C₆-C₂₄arylcarbonyloxy (—O—CO-aryl)), C₂-C₂₄ alkoxycarbonyl (—(CO)—O-alkyl),C₆-C₂₄ aryloxycarbonyl (—(CO)—O-aryl), halocarbonyl (—CO)—X where X ishalo), C₂-C₂₄ alkylcarbonato (—O—(CO)—O-alkyl), C₆-C₂₄ arylcarbonato(—O—(CO)—O-aryl), carboxy (—COOH), carboxylato (—COO⁻), carbamoyl(—(CO)—NH₂), mono-(C₁-C₂₄ alkyl)-substituted carbamoyl (—(CO)—NH(C₁-C₂₄alkyl)), di-(C₁-C₂₄ alkyl)-substituted carbamoyl (—(CO)—N(C₁-C₂₄alkyl)₂), mono-(C₁-C₂₄ haloalkyl)-substituted carbamoyl (—(CO)—NH(C₁-C₂₄haloalkyl)), di-(C₁-C₂₄ haloalkyl)-substituted carbamoyl (—(CO)—N(C₁-C₂₄haloalkyl)₂), mono-(C₅-C₂₄ aryl)-substituted carbamoyl (—(CO)—NH-aryl),di-(C₅-C₂₄ aryl)-substituted carbamoyl (—(CO)—N(C₅-C₂₄ aryl)₂),di-N—(C₁-C₂₄ alkyl), N—(C₅-C₂₄ aryl)-substituted carbamoyl(—(CO)—N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl), thiocarbamoyl (—(CS)—NH₂),mono-(C₁-C₂₄ alkyl)-substituted thiocarbamoyl (—(CS)—NH(C₁-C₂₄ alkyl)),di-(C₁-C₂₄ alkyl)-substituted thiocarbamoyl (—(CS)—N(C₁-C₂₄ alkyl)₂),mono-(C₅-C₂₄ aryl)-substituted thiocarbamoyl (—(CS)—NH-aryl), di-(C₅-C₂₄aryl)-substituted thiocarbamoyl (—(CS)—N(C₅-C₂₄ aryl)₂), di-N—(C₁-C₂₄alkyl), N—(C₅-C₂₄ aryl)-substituted thiocarbamoyl (—(CS)—N(C₁-C₂₄alkyl)(C₅-C₂₄ aryl), carbamido (—NH—(CO)—NH₂), cyano (—C≡N), cyanato(—O—≡N), thiocyanato (—S—C≡N), isocyanate (—N═C═O), thioisocyanate(—N═C═S), formyl (—(CO)—H), thioformyl (—(CS)—H), amino (—NH₂),mono-(C₁-C₂₄ alkyl)-substituted amino (—NH(C₁-C₂₄ alkyl), di-(C₁-C₂₄alkyl)-substituted amino (—N(C₁-C₂₄ alkyl)₂), mono-(C₅-C₂₄aryl)-substituted amino (—NH(C₅-C₂₄ aryl), di-(C₅-C₂₄ aryl)-substitutedamino (—N(C₅-C₂₄ aryl)₂), C₂-C₂₄ alkylamido (—NH—(CO)-alkyl), C₆-C₂₄arylamido (—NH—(CO)-aryl), imino (—CR═NH where R includes withoutlimitation hydrogen, C₁-C₂₄ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄aralkyl, etc.), C₂-C₂₀ alkylimino (—CR═N(alkyl), where R includeswithout limitation hydrogen, C₁-C₂₄ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl,C₆-C₂₄ aralkyl, etc.), arylimino (—CR═N(aryl), where R includes withoutlimitation hydrogen, C₁-C₂₀ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄aralkyl, etc.), nitro (—NO₂), nitroso (—NO), sulfo (—SO₂—OH), sulfonato(—SO₂—O⁻), C₁-C₂₄ alkylsulfanyl (—S-alkyl; also termed “alkylthio”),C₅-C₂₄ arylsulfanyl (—S-aryl; also termed “arylthio”), C₁-C₂₄alkylsulfinyl (—(SO)-alkyl), C₅-C₂₄ arylsulfinyl (—(SO)-aryl), C₁-C₂₄alkylsulfonyl (—SO₂-alkyl), C₁-C₂₄ monoalkylaminosulfonyl (—SO₂—N(H)alkyl), C₁-C₂₄ dialkylaminosulfonyl (—SO₂—N(alkyl)₂), C₅-C₂₄arylsulfonyl (—SO₂-aryl), boryl (—BH₂), borono (—B(OH)₂), boronato(—B(OR)₂ where R is alkyl or aryl), phosphono (—P(O)(OH)₂), phosphonato(—P(O)(O⁻)₂), phosphinato (—P(O)(O⁻)), phospho (—PO₂), and phosphino(—PH₂); and the hydrocarbyl moieties C₁-C₂₄ alkyl (preferably C₁-C₁₂alkyl, more preferably C₁-C₆ alkyl), C₅-C₂₄ aryl (preferably C₅-C₁₄aryl), C₆-C₂₄ alkaryl (preferably C₆-C₁₆ alkaryl), and C₆-C₂₄ aralkyl(preferably C₆-C₁₆ aralkyl).

Olefin Reactant Comprising Two Terminal Olefins

One or more olefin reactants comprising a reactant olefin may be usedwith the invention described herein, wherein the olefin reactantcomprises two terminal olefins (i.e., a diene) wherein the olefinreactant is brought into contact in the presence of a catalyticallyeffective amount of the metal carbene olefin metathesis catalyst, underconditions and for a time period effective to allow the cross metathesisreaction to occur.

An example of an olefin reactant comprising two terminal olefins (i.e.,a diene) is a diene represented by the structure of Formula (J):

wherein:

J* and V* are independently selected from C₁-C₂₀ alkylene andsubstituted C₁-C₂₀ alkylene; T* is selected from nil, carbonyl (—C═O),carboxyl (—C(O)—O—), carbamoyl (—C(O)—NH—) and amino (—NH—), or—C(R^(T7))(R^(T8))—; R^(T1), R^(T2), R^(T3), R^(T4), R^(T5), R^(T6),R^(T7), and R^(T8) are independently selected from hydrogen, hydrocarbyl(e.g., C₁-C₂₀ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl),substituted hydrocarbyl (e.g., substituted C₁-C₂₀ alkyl, C₅-C₂₄ aryl,C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl), heteroatom-containing hydrocarbyl(e.g., heteroatom-containing C₁-C₂₀ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl,C₆-C₂₄ aralkyl), and substituted heteroatom-containing hydrocarbyl(e.g., substituted heteroatom-containing C₁-C₂₀ alkyl, C₅-C₂₄ aryl,C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl), and functional groups, wherein thesubstituent groups are selected from functional groups selecte from thegroup consisting of halo, hydroxyl, sulfhydryl, C₁-C₂₄ alkoxy, C₅-C₂₄aryloxy, C₆-C₂₄ aralkyloxy, C₆-C₂₄ alkaryloxy, acyl (including C₂-C₂₄alkylcarbonyl (—CO-alkyl) and C₆-C₂₄ arylcarbonyl (—CO-aryl)), acyloxy(—O—acyl, including C₂-C₂₄ alkylcarbonyloxy (—O—CO-alkyl) and C₆-C₂₄arylcarbonyloxy (—O—CO-aryl)), C₂-C₂₄ alkoxycarbonyl (—(CO)—O-alkyl),C₆-C₂₄ aryloxycarbonyl (—(CO)—O-aryl), halocarbonyl (—CO)—X where X ishalo), C₂-C₂₄ alkylcarbonato (—O—(CO)—O-alkyl), C₆-C₂₄ arylcarbonato(—O—(CO)—O-aryl), carboxy (—COOH), carboxylato (—COO⁻), carbamoyl(—(CO)—NH₂), mono-(C₁-C₂₄ alkyl)-substituted carbamoyl (—(CO)—NH(C₁-C₂₄alkyl)), di-(C₁-C₂₄ alkyl)-substituted carbamoyl (—(CO)—N(C₁-C₂₄alkyl)₂), mono-(C₁-C₂₄ haloalkyl)-substituted carbamoyl (—(CO)—NH(C₁-C₂₄haloalkyl)), di-(C₁-C₂₄ haloalkyl)-substituted carbamoyl (—(CO)—N(C₁-C₂₄haloalkyl)₂), mono-(C₅-C₂₄ aryl)-substituted carbamoyl (—(CO)—NH-aryl),di-(C₅-C₂₄ aryl)-substituted carbamoyl (—(CO)—N(C₅-C₂₄ aryl)₂),di-N—(C₁-C₂₄ alkyl),N—(C₅-C₂₄ aryl)-substituted carbamoyl(—(CO)—N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl), thiocarbamoyl (—(CS)—NH₂),mono-(C₁-C₂₄ alkyl)-substituted thiocarbamoyl (—(CS)—NH(C₁-C₂₄ alkyl)),di-(C₁-C₂₄ alkyl)-substituted thiocarbamoyl (—(CS)—N(C₁-C₂₄ alkyl)₂),mono-(C₅-C₂₄ aryl)-substituted thiocarbamoyl (—(CS)—NH-aryl), di-(C₅-C₂₄aryl)-substituted thiocarbamoyl (—(CS)—N(C₅-C₂₄ aryl)₂), di—N—(C₁-C₂₄alkyl), N—(C₅-C₂₄ aryl)-substituted thiocarbamoyl (—(CS)—N(C₁-C₂₄alkyl)(C₅-C₂₄ aryl), carbamido (—NH—(CO)—NH₂), cyano (—C≡N) , cyanato(—O—C≡N), thiocyanato (—S—C≡N), isocyanate (—N═C═O), thioisocyanate(—N═C═S), formyl (—(CO)—H), thioformyl (—(CS)—H), amino (—NH₂),mono-(C₁-C₂₄ alkyl)-substituted amino (—NH(C₁-C₂₄ alkyl), di-(C₁-C₂₄alkyl)-substituted amino (—N(C₁-C₂₄ alkyl)₂), mono-(C₅-C₂₄aryl)-substituted amino (—NH(C₅-C₂₄ aryl), di-(C₅-C₂₄ aryl)-substitutedamino (—N(C₅-C₂₄ aryl)₂), C₂-C₂₄ alkylamido (—NH—(CO)-alkyl), C₆-C₂₄arylamido (—NH—(CO)-aryl), imino (—CR═NH where R includes withoutlimitation hydrogen, C₁-C₂₄ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄aralkyl, etc.), C₂-C₂₀ alkylimino (—CR═N(alkyl), where R includeswithout limitation hydrogen, C₁-C₂₄ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl,C₆-C₂₄ aralkyl, etc.), arylimino (—CR═N(aryl), where R includes withoutlimitation hydrogen, C₁-C₂₀ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄aralkyl, etc.), nitro (—NO₂), nitroso (—NO), sulfo (—SO₂—OH), sulfonato(—SO₂—O⁻), C₁-C₂₄ alkylsulfanyl (—S-alkyl; also termed “alkylthio”),C₅-C₂₄ arylsulfanyl (—S-aryl; also termed “arylthio”), C₁-C₂₄alkylsulfinyl (—(SO)-alkyl), C₅-C₂₄ arylsulfinyl (—(SO)-aryl), C₁-C₂₄alkylsulfonyl (—SO₂-alkyl), C₁-C₂₄ monoalkylaminosulfonyl (13 SO₂—N(H)alkyl), C₁-C₂₄ dialkylaminosulfonyl (—SO₂—N(alkyl)₂), C₅-C₂₄arylsulfonyl (—SO₂-aryl), boryl (—BH₂), borono (—B(OH)₂), boronato(—B(OR)₂ where R is alkyl or aryl), phosphono (—P(O)(OH)₂), phosphonato(—P(O)(O⁻)₂), phosphinato (—P(O)(O⁻)), phospho (—PO₂), and phosphino(—PH₂); and the hydrocarbyl moieties C₁-C₂₄ alkyl (preferably C₁-C₁₂alkyl, more preferably C₁-C₆ alkyl), C₅-C₂₄ aryl (preferably C₅-C₁₄aryl), C₆-C₂₄ alkaryl (preferably C₆-C₁₆ alkaryl), and C₆-C₂₄ aralkyl(preferably C₆-C₁₆ aralkyl); R^(T1), R^(T2), R^(T3), R^(T4), R^(T5),R^(T6), R^(T7), R^(T8), and functional groups cannot contain olefiniccarbon-carbon double bonds (i.e., —C═C—) or carbon-carbon triple bonds(i.e., —C≡C—).

Any two of R^(T1), R^(T2), R^(T3), R^(T4), R^(T5), R^(T6), R^(T7), andR^(T8) may also be linked to form a cyclic group, which may be aliphaticor aromatic, and may contain substituents and/or heteroatoms. Generally,such a cyclic group will contain 4 to 12, preferably 5, 6, 7, or 8 ringatoms. The cyclic group and any substituents cannot contain olefiniccarbon-carbon double bonds (i.e., —C═C—) or carbon-carbon triple bonds(i.e., —C≡C—).

It is to be understood that while the invention has been described inconjunction with specific embodiments thereof, that the descriptionabove as well as the examples that follow are intended to illustrate andnot limit the scope of the invention. Other aspects, advantages, andmodifications within the scope of the invention will be apparent tothose skilled in the art to which the invention pertains.

EXAMPLES

The following examples are for illustrative purposes only and are notintended, nor should they be construed as limiting the invention in anymanner. Those skilled in the art will appreciate that variations andmodifications of the following examples can be made without exceedingthe spirit or scope of the invention.

All reactions involving metal complexes were conducted in oven-driedglassware under an argon or nitrogen atmosphere using standard Schlenktechniques. Chemicals and solvents were obtained from Sigma-Aldrich,Strem, Afla Aesar, Nexeo, Brenntag, AG Layne and TCI. Commerciallyavailable reagents were used as received unless otherwise noted. Silicagel was purchased from Fisher (0.040-0.063 μm, EMD Millipore).

Cyclic olefin metathesis catalysts were prepared by standard methods andinclude:[1,3-bis[2-(1-methylethyl)phenyl]-2-imidazolidinylidene]dichloro(phenylmethylene)(tricyclohexylphosphine) Ruthenium(II) (C849); [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene] dichloro (phenylmethylene) (tricyclohexylphosphine) Ruthenium(II) (C848); dichloro(phenylmethylene)bis(tricyclohexylphosphine) Ruthenium(II) (C823);dichloro(2-(1-methylethoxy)phenyl]methylene) (tricyclohexylphosphine)Ruthenium(II) (C601).

¹H and ¹³C NMR spectra were recorded.

Volatile products were analyzed using an Agilent 6850 gas chromatography(GC) instrument with a flame ionization detector (FID). The followingconditions and equipment were used:

-   -   Column: HP-5, 30 m×0.25 mm (ID)×0.25 μm film thickness.    -   Manufacturer: Agilent    -   GC conditions: Injector temperature: 250° C.        -   Detector temperature: 280° C.    -   Oven temperature: Starting temperature: 100° C., hold time: 1        minute.        -   Ramp rate 10° C./min to 250° C., hold time: 12 minutes.    -   Carrier gas: Helium    -   Mean gas velocity: 31.3±3.5% cm/sec (calculated)    -   Split ratio: ˜50:1

The products were characterized by comparing peaks with known standards,in conjunction with supporting data from mass spectrum analysis(GCMS-Agilent 5973N). GCMS analysis was accomplished with a second HP-5,30 m×0.25 mm (ID)×0.25 μm film thickness GC column, using the samemethod as above.

The following abbreviations are used in the examples and throughout thespecification:

DCM/CH₂Cl₂ dichloromethane rt room temperature CDCl₃ deuteratedchloroform CD₂Cl₂ deuterated dichloromethane C₆D₆ deuterated benzeneC₆H₆ benzene C848

[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(phenylmethylene) (tricyclohexylphosphine)Ruthenium(II) CAS [246047-72-3] C849

[1,3-bis[2-(1-methylethyl)phenyl]- 2-imidazolidinylidene]dichloro(phenylmethylene)(tricyclohexylphosphine) Ruthenium(II) CAS[936715-64-9] C823

dichloro(phenylmethylene) bis(tricyclohexylphosphine) Ruthenium(II) CAS[172222-30-9] C601

dichloro(2-(1-methylethoxy)phenyl]methylene) (tricyclohexylphosphine)Ruthenium(II) CAS [203714-71-0] Cy cyclohexyl RCM ring closingmetathesis ROCM ring opening cross metathesis ROMP ring openingmetathesis polymerization CM cross metathesis NHC N-heterocyclic carbenemin minutes gas chromatography GC PPh₃MeBr methyltriphenylphosphoniumbromide NaH sodium hydride Pd/C palladium on carbon H₂ hydrogen Al(OPh)₃tri-phenoxy aluminum NaBH₄ sodium borohydride c-HCl concentratedhydrochloride acid HC(OEt)₃ tri-ethylorthoformate NH₄BF₄ ammoniumtetrafluoroborate KOtBu potassium tert-butoxide [Me₃Si]₂NK potassiumbis(trimethylsilyl)azide DBB 1,4-dibenzoyloxy-2-butene BTBB1,4-bis(triisopropylbenzoyloxy)-2-butene C₆H₆ benzene C₆D₆ deuteratedbenzene rac racemic

The following experimental methods illustrate how compounds according tothe invention were made. Those skilled in the art will routinely be ableto modify and/or adapt the following methods to synthesize any compoundof the invention.

Example 1 The Synthesis of Catalysts Example 1a The Synthesis ofCatalyst (3)-rac

The synthesis of catalyst (3)-rac is shown in Scheme 4.ortho-Phenethylaniline (5) was prepared either through Friedel-Craftreaction from aniline, or Wittig reaction/reduction from compound (4).Condensation of two molecules of (5) with glyoxal, followed byborohydride reduction produced the bis-amine (6) as a mixture of mesoand racemic isomers. After separation of the two isomers by columnchromatography on silica-gel, crystal structures of both products wereobtained to solve their relative stereochemistry. We first chose theracemic isomer of bis-amine amine (6) as NHC ligand, due its C₂ symmetryand its steric effects, which would predict the formation of the (E)isomer in our model. Cyclization of (6)-rac provided the NHC salt(7)-rac in high yield. Due to the sterics on ligand (7)-rac, NHC salt,the ligand exchange on catalyst C823 (1) took a long time to complete (6h at 50° C.), however, catalyst (3)-rac was successfully obtained inhigh yield (71%) and high purity after chromatography on neutralsilica-gel or neutral alumina.

Catalyst (3)-meso was synthesized according to the procedure used forthe synthesis of Catalyst (3)-rac, using the meso isomer of theNHC-ligand (7).

Example 1b The Synthesis of Catalyst (16)

The synthesis of catalyst (16)-rac is shown in Scheme 5. Reaction ofcatalyst C601 (15) with NHC ligand (7)-rac (1.1 equivalents) in thepresence of KOtBu (1.1 equivalents) in C₆H₆, followed by removal of thesolvent under vacuum and purification through column chromatography onsilica using dichloromethane as the eluent, yielded catalyst (16)-rac asa green solid. X-ray crystallography (FIG. 9), was used to confirm thestructure of this catalyst. The ortho-substituents of the N-aryl groupsare oriented such that the NHC ligand bound to the catalyst gave apseudo-C₂-symmetry. One N-aryl group lies directly over the Ru═C bondand lies almost perpendicular to the plane of the aryl group of thebenzylidene moiety.

Catalyst (16)-meso was synthesized according to the procedure used forthe synthesis of Catalyst (16)-rac, using the meso isomer of theNHC-ligand (7).

Example 2 Ring Closing Metathesis Reactions Example 2a Synthesis ofCyclopentene (9)

The ring closing metathesis activity of new ruthenium complex (3)-rac,was demonstrated with diethyl diallylmalonate (8). An efficient RCMreaction occurred yielding cyclopentene (9) in quantitate yield (Scheme6).

We also studied the kinetics of catalyst (3)-rac by ¹H-NMR in the RCMreaction of (8). As shown in FIG. 5, C848 (2) and catalyst (3)-rac havenearly identical activity profiles. Moreover, the logarithmic plot (FIG.6) is linear, indicating pseudo-first-order kinetics over the course ofthe reaction. A curvature in the logarithmic plot would be consistentwith catalyst decomposition.

Example 2b Macrocyclic Ring Closing Metathesis Catalyzed by (3)-rac

The ability of new ruthenium complex (3)-rac was compared with 2^(nd)generation catalyst C848 (2) in the macrocyclic ring closing olefinmetathesis of diene (10) (Scheme 7). Monitoring the reaction progress bygas chromatography (GC) before 100% conversion was critical to establishthe reaction's kinetic profile. In the presence of new ruthenium complex(3)-rac, the reaction yields RCM product (11) with an (E/Z) ratio of13:1 at 80% conversion while 2^(nd) generation catalyst C848 (2)provides an (E/Z) ratio of 10:1 at 84% conversion. The result indicatedthat new ruthenium complex (3)-rac is slightly more in favor to provide(E)-selective macrocyclic RCM products than (2).

Example 3 Ring Opening Cross Metathesis Reactions (ROCM) and RingOpening Metathesis Polymerization Reactions (ROMP) Example 3a RingOpening Cross Metathesis of Norbornene Diacetate (12) with Styrene

Evaluating the (E/Z) selectivity at early conversion is critical sinceit provides direct insight to kinetic selectivity. We compared the ROCMof norbornene diacetate (12) with styrene in the presence of catalystsC848 (2) and catalyst (3)-rac (Scheme 8).

The evolution of the reaction described in Scheme 8 was monitored by GC.The results are shown in FIGS. 2, 3, and 4. FIGS. 2, 3, and 4 summarizethe results for the two catalysts examined: C848 (2) and catalyst(3)-rac. In FIG. 2, the chosen reaction conditions provide a reactionenvironment where the reaction progress can be efficiently monitored. Asillustrated in FIG. 3, at 36% conversion, C848 (2) shows an (E/Z)selectivity of 1.2/1. In comparison, at 34% conversion, catalyst (3)-racshows an (E/Z) selectivity of 2.1:1.

A comparison of selectivity versus time is shown in FIG. 4. For catalystC848 (2) and catalyst (3)-rac, the (E/Z) ratio remains constantthroughout the course of the reaction. This is an indication thatcatalyst (3)-rac is kinetically more selective than C848 (2) for the (E)form of the ROCM product (13). Thus, a 100% increase in selectivity hasbeen achieved.

Example 3b Ring Opening Metathesis Polymerization of Cyclooctene WithStyrene

A similar increase in selectivity was observed for the reactiondescribed in Scheme 9. At 25% conversion, C848 (2) produced the ROMPproduct (14) with an (E/Z) ratio of 4:1. At that same conversion,catalyst (3)-rac gave an (E/Z) ratio of 7:1. Empirical data indicatethat the thermodynamic ratio for this reaction is an (E/Z) ratio of 4:1.FIG. 7 summarizes the conversion in ROMP of cyclooctene using C848 (2)and catalyst (3)-rac. FIG. 8 summarizes the Log plots for catalyst C848(2) and catalyst (3)-rac in the ROMP of cyclooctene.

Catalyst (3)-rac gives us insight into other promising ligand scaffoldsthat could be synthesized to improve both catalyst selectivity andactivity for ROCM and basic CM reactions. Tuning the structure of thesecatalysts such that steric impedances allow for the formation of thedesired stereochemistry may allow us to achieve this goal. Modificationof the robust and easily tuned NHC ligand will be the key to controllingstereoselectivity. For example, by connecting the sub stituents on theortho positions of each aryl group to make a tether in the NHC ligandsmay improve the selectivity. It is also hoped that the use of a bulkythiol ligand in place of one of the chlorides may result in pushing thetwo ortho groups to the same side and would also provide a steric blockfor the C3 position on the metallacycle to fit the model shown above.

Example 4 Cross Metathesis Reactions Example 4a Cross Metathesis of5-decene with di-benzoate Substrates

The cross metathesis reaction (Scheme 10) of 5-decene with (18) DBB andcross metathesis reaction (Scheme 11) of 5-decene with (20) BTBB usingruthenium catalysts, have been monitored by ¹H NMR. As shown in FIGS. 11and 12, the ¹H peaks on the allylic position of the (E) and (Z) formsare well distinguished from each other in the (18) and (20) substrates,as well as in the and the corresponding products (19) and (21). Hence,¹H NMR array experiments can illustrate the change of (E/Z) selectivityover the duration of the reaction.

5-Decene and (18) DBB were dissolved in dry C₆D₆ to give a 0.12 Msolution with a 3:1 ratio of 5-decene to (18) DBB. 0.0066 M of rutheniumcatalyst solution in dry C₆D₆ was prepared in a separate vial. In a dryNMR tube containing 0.55 mL of the above substrate solution was added anadequate amount of ruthenium catalyst solution right before starting the¹H NMR study. ¹H NMR experiments were ran for 4 h at room temperature,performing a ¹H NMR spectra every 10 minutes (600 MHz, Varian NMR, setwith 45° pulse angle and 2 second relaxation delay).

The results of the ¹H NMR study were summarized in Tables 2, 3, and 4and FIGS. 13 and 14. As shown in the results, catalyst (3)-rac providedthe cross metathesis product with slightly higher (E/Z) ratio thancatalyst (2) in all of reactions studied. In addition, the (E) forms of(18) DBB and (20) BTBB gave a higher (E/Z) ratio of the products (19)and (21) respectively compared to the same reactions with the (Z) forms.

TABLE 2 (E/Z) Ratio of product (19) in the cross metathesis reaction of(Z)-5-decene with (Z)-(18) DBB (E/Z) ratio of (19) at Entry Catalyst Mol% % Cony. (4 h) 60% conversion 1 C848 (2) 2 60 4.1 2 C848 (2) 5 67 4.2 3(3)-rac 2 90 ~6 4 (3)-rac 1 74 5.8 5 (3)-rac 0.7 61 5.8 6 (3)-meso 2 544.9* 7 C849 2 70 4.4 * at 54% conversion

TABLE 3 (E/Z) Ratio of product (19) in the cross metathesis reaction of5-decene with (18) DBB Cat. 2% Conv. (E/Z) ratio of (19) Entry Mol5-Decene (18) DBB (4 h) at 40% conversion 1 C848 (2) (Z) (E) 48 6.2 2C848 (2) (E) (E) 54 6.3 3 C848 (2) (E) (Z) 63 2.7 4 (3)-rac (Z) (E) 426.8 5 (3)-rac (E) (E) 44 6.9 6 (3)-rac (E) (Z) 77 ~4 7 (3)-meso (E) (E)40 6.9

TABLE 4 (E/Z) Ratio of product (21) in the cross metathesis reaction of5-decene with (20) BTBB Cat. 2% Conversion (E/Z) ratio Entry Mol5-Decene (20) BTBB (4 h) of (21) 1 C848 (2) (Z) (Z) 82 ~4* 2 (3)-rac (Z)(Z) 79 ~5* 3 C848 (2) (E) (E) 83     7.2** 4 (3)-rac (E) (E) 55    7.5** *at 60% conversion **at 50% conversion

Extension of these catalysts to the (E)-selective olefin metathesis willenable an elegant approach to the application of natural productsynthesis and pharmaceutical area.

What is claimed is:
 1. A compound represented by Formula (IV):

wherein: M is a Group 8 transition metal; R^(V1), R^(V2), R^(V3),R^(V4), and R^(V5) are independently hydrogen, substituted branchedC₁-C₆ alkyl, C₄-C₁₀ cycloalkyl, substituted C₄-C₁₀ cycloalkyl, C₄-C₁₀heteroatom-containing cycloalkyl, substituted C₄-C₁₀heteroatom-containing cycloalkyl, C₅-C₁₄ aryl, substituted C₅-C₁₄ aryl;R¹¹, R¹², R^(11a), and R^(12a) are independently hydrogen, C₁-C₁₂ alkyl,substituted C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy, substituted C₁-C₁₂ alkoxy,C₅-C₁₄ aryl, substituted C₅-C₁₄ aryl, or halide; X¹ and X² areindependently halogen; L² and L³ are neutral electron donor ligands,wherein L² and/or L³ may be linked with R¹ or R² to form one or morecyclic groups; n is 0 or 1; m is 0, 1, or 2; k is 0 or 1; R¹ and R² areindependently selected from hydrogen, hydrocarbyl, substitutedhydrocarbyl, heteroatom-containing hydrocarbyl, substitutedheteroatom-containing hydrocarbyl; at least one of R^(V1), R^(V2),R^(V3), R^(V4), or R^(V5) is represented by a group such as:

“a” represents 0, 1, 2, 3, 4, or 5; and R is substituted C₁-C₆ alkyl,C₁-C₆ alkyl, substituted C₃-C₁₀ cycloalkyl, C₃-C₁₀ cycloalkyl, orhalogen.
 2. The compound according to claim 1, wherein M is Ru; n is 0;m is 0; k is 1; X¹ and X² are independently halogen; L² is a neutralelectron donor ligand; and R¹¹, R¹², R^(11a), and R^(12a) areindependently hydrogen.
 3. The compound according to claim 2, wherein:R^(V1), R^(V2), R^(V3), R^(V4), and R^(V5) are independently hydrogen orsubstituted branched C₁-C₆ alkyl; and at least one of R^(V1), R^(V2),R^(V3), R^(V4), or R^(V5) is represented by a group such as:


4. The compound according to claim 3, wherein: R^(V1), R^(V2), R^(V3),and R^(V4) are independently hydrogen; X¹ and X² are independentlychloride; L² is PCy3; R¹ is hydrogen; R² is phenyl; R^(V5) is

and “a” is
 0. 5. A compound represented by Formula (VII):

wherein: M is Ru or Os; R^(V1), R^(V2), R^(V3), R^(V4), and R^(V5) areindependently hydrogen, substituted branched C₁-C₆ alkyl, C₄-C₁₀cycloalkyl, substituted C₄-C₁₀ cycloalkyl, C₄-C₁₀ heteroatom-containingcycloalkyl, substituted C₄-C₁₀ heteroatom-containing cycloalkyl, C₅-C₁₄aryl, substituted C₅-C₁₄ aryl; R¹¹, R¹², R^(11a), and R^(12a) areindependently hydrogen, C₁-C₁₂ alkyl, substituted C₁-C₁₂ alkyl, C₁-C₁₂alkoxy, substituted C₁-C₁₂ alkoxy, C₅-C₁₄ aryl, substituted C₅-C₁₄ aryl,or halide; X¹ and X² are independently halogen; Y is a heteroatomselected from N, O, S, and P; R⁵, R⁶, R⁷, and R⁸ are each,independently, selected from the group consisting of hydrogen, halogen,alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom containingalkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy,alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl,monoalkylaminosulfonyl, dialkylaminosulfonyl, alkyl sulfonyl, nitrile,nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid,ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether,amine, imine, amide, halogen-substituted amide, trifluoroamide, sulfide,disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate,borate; n is 0, 1, or 2; Z is a group selected from hydrogen, alkyl,aryl, functionalized alkyl, functionalized aryl; and at least one ofR^(V1), R^(V2), R^(V3), R^(V4), or R^(V5) is represented by a group suchas:

“a” represents 0, 1, 2, 3, 4, or 5; and R is substituted C₁-C₆ alkyl,C₁-C₆ alkyl, substituted C₃-C₁₀ cycloalkyl, C₃-C₁₀ cycloalkyl, orhalogen.
 6. The compound according to claim 5 wherein: M is Ru; X¹ andX² are each chloride; Y is 0; R⁵, R⁶, R⁷, and R⁸ are each hydrogen; n is1; Z is iso-propyl; R^(V1), R^(V2), R^(V3), and R^(V4) are independentlyhydrogen; R¹¹, R¹², R^(11a), and R^(12a) are independently hydrogen;R^(V5) is

and “a” represents
 0. 7. A method for performing a metathesis reactioncomprising, contacting at least one olefin with a compound of Formula(IV) or Formula (VII).
 8. The method according to claim 7, wherein themetathesis reaction is a ring closing metathesis reaction.
 9. The methodaccording to claim 7, wherein the metathesis reaction is a ring openingcross metathesis reaction.
 10. The method according to claim 7, whereinthe metathesis reaction is a cross metathesis reaction.
 11. The methodaccording to claim 7, wherein the metathesis reaction is a ring openingmetathesis polymerization reaction.
 12. The method according to claim11, wherein the ring opening metathesis polymerization reactioncomprises at least one cyclic olefin reactant.
 13. The method accordingto claim 10, wherein the cross metathesis reaction comprises at leastone reactant internal olefin.
 14. The compound according to claim 1,wherein the compound may be in a racemic isomeric form, a meso isomericform, or a mixture of the racemic and meso isomeric forms.
 15. Thecompound according to claim 3, wherein the compound may be in a racemicisomeric form, a meso isomeric form, or a mixture of the racemic andmeso isomeric forms.
 16. The compound according to claim 1, wherein thecompound is selected from:


17. The compound according to claim 16, wherein the compound may be in aracemic isomeric form, a meso isomeric form, or a mixture of the racemicand meso isomeric forms.
 18. The method according to claim 7, whereinthe compound of Formula (IV) may be in a racemic isomeric form, a mesoisomeric form, or a mixture of the racemic and meso isomeric forms. 19.The method according to claim 7, wherein the compound of Formula (IV) isselected from:


20. The method according to claim 19, wherein the compound may be in aracemic isomeric form, a meso isomeric form, or a mixture of the racemicand meso isomeric forms.